Catalysis in a Refinery. Hartmut Schütter

Transcription

1 Catalysis in a Refinery artmut Schütter

2 Boiling Range of Crude Oil (REB) Boiling Temperature C ,2% LPG 16% Naphtha 10% Kero 32% Diesel / EL appr. 50% atm. residue 33% Vacuumgasoils 17% Vacuumresidue (eavy Fuel oil/bitumen) wt% Figure 1

3 Crude Oil Distillation atm. Distillation Crude Oil Gas/ LPG Light Naphthas Mid/eavy Naphtha Middledistillates Steam Cracker Fuel Steamreformer(2) Isomerization(Gasoline Pool) Steam Cracker Cat Reformer(Aromatics) Cat Reformer(Gasoloine Pool) ydrotreater(jet Fuel) ydrotreater(diesel/domestic FuelOil) VGO ydrotreater/cat Cracker Vacuumdistillation Vacuum residue(bitumn/eavy Fuel Oil Figure 2

4 Demand of Oil Products differs from Composition of Crude Oil Boiling Temperature C Technical Services PCK crude oil R ussian E xport B lend 32.4 API 1.5 %S market demand Percentage wt% Refining Figure 3

5 50 Crude Oil Kero atmosph. Residue S > 3% Propane Butane 1.2 Naphtha RON<50 S>500ppm Gasoil S > 1% Propane Jet eavy Fuel Oil S<1% Propylene Butane 5 Gasoline RON S<10ppm EL 5 Refinery Target Yields 30 Diesel S<10ppm Cetan No Figure 4

6 Refiner/reformer isomerization Jet fuel hydrotreating MD hydrotreating DESUS / FCC / Alkylation / ETBE ETBE Claus units Figure 5

7 Gasoline Upgrading Increasement of Octane number by Isomerization Conversion of normal C 5 /C 6 Paraffins to iso Paraffins Increasement of Octane number by catalytic Reforming Aromatics from Dehydrogenation of Naphthenes as well as Dehydrocyclisation of Paraffins Increasement of Octane number by Alkylation Conversion of iso C 4 with Butenes to iso Octane Increasement of Octane number by Etherification Conversion of iso Butene with Ethanol to ETBE Figure 6

8 Figure 7 Antiknock Property Octane number = Vol% n-eptane Octane number = Vol% iso-octane Octane number C C C C C C C - C - C C C C C - C - - C -

9 Light Naphtha Isomerization Figure 8

10 Catalytic Reforming Figure 9

11 Ether Figure 10

12 Refiner/reformer isomerization Jet fuel hydrotreating DESUS / FCC / Alkylation / ETBE ETBE MD hydrotreating Claus units Figure 11

13 Development of Sulfur Limit in Gasoline Sulfur in ppm bis Figure 12

14 Development of Sulfur Limit in Diesel Fuels Sulfur in ppm past 80/ Figure 13

15 Diesel ydrotreating Figure 14

16 Increasing of Desulfurization from 95 % up to more than 99.9 % with existing ydrotreaters by increasing of Reactortemperature only? > + 40 C WABT Reactor outlet temperature > 400 C material? Cycle length Productstability (color, ox.stab.) target sulfur critical ( ppm recombination to RS, Thiophene) Figure 15

17 AOP - Targets Reliability Flexibility Potential to future Low opex (not lowest investment) Improved margin Figure 16

18 ydrogen partial pressure in the reactor p 2, bar Recycle gas ratio 250 Nm³/m³ p Reactor 2 bar P 2S =1,86bar > 50% higher reaction rate constant Recycle gas ratio 150 Nm³/m³ p Reactor 4 bar catalyst bed length relativ, % P 2S =3,92bar Figure 17

19 Basic desulfurization reactions sulfides > thiophenes > benzothiophenes > dibenzothiophenes Figure 18

20 DS - Kinetic k LSV 1 1 = n 1 n n 1 S S ,0% DS LSV = 1 x 99,9% DS LSV = 0.33 x Cat requirement 3 times more Figure 19

21 DK 4 R2 weight 535 t d a = 4.6 m s = 98 mm h = 43.5 m Figure 20

22 DK4 Reactors R-901 and R-902 Quenchgas 352 C :30: m³/h 329 t/h knm³/h 325 C bar R-902 p=0.56 bar 352 C 353 C 352 C R-901 p=0.26 bar 325 C 325 C 326 C 338 C 338 C 339 C 356 C 357 C 357 C 356 C 357 C 358 C 338 C 338 C 340 C 360 C 360 C 360 C 361 C 361 C 360 C 354 C 353 C 352 C 361 C 363 C 362 C 357 C T (R-901)=33 K 363 C T (R-902)=11 K 7.1 weight ppm S WABT (R-901 & R-902)=350 C Figure 21

23 DK 4 Reactor pressure drop pressure drop of R R 902 (bar) Technical Services PCK 0.2 bar per 30 months < < 0.01 bar per month Jan-01 Apr-01 Jul-01 Nov-01 Feb-02 May-02 Sep-02 Dec-02 Mar-03 Jun-03 Oct-03 Figure 22

24 R M P C T - DK4 (Robust Multivariable Predictive Control Technology) :02:46 controlerstatus: ON Set points (Sollwerte): Feed heater outlet temperature O-901 FC9011: TC9027: actual vorausber. min. max. Status 385 t/h 385 t/h 365 t/h 385 t/h MV is ON 321 C 321 C 316 C 362 C MV is ON Monitored points: aktuell vorausber. min. max. Status pressure Feed control valve FC bar 1 bar 1 bar 6 bar GOOD Max. Skintemperature O C 403 C 0 C 460 C GOOD Max. combustion chambertemperature O C 644 C 0 C 700 C GOOD Opening control valve fuelgas to O % 71% 10% 95% GOOD Max. Reactortemperature 365 C 364 C 0 C 380 C GOOD Ampere V A 1059 A 0 A 1230 A GOOD Raffinate sulfur 6.81 ppm 7,20 ppm 0,00 ppm 7,20 ppm GOOD Comparison measurement/calculated: Suflur analyzed: 6.82 ppm Sulfur calculated (corr.): 6.81 ppm Sulfur caculated (uncorr): 6.37 ppm Figure 23

25 DK 4 Advanced Control (RMPCT) Sulfur content of raffinate, ppm Set points actual data Feb.02 Mrz.02 Apr.02 Jun.02 Jul.02 Aug.02 Okt.02 Nov.02 Figure 24

26 Sulfur content, ppm Changeover fuel quality from 50 to < 10 ppm Sulfur Supply 4 ppm Supply 9 ppm days Figure 25

27 DK 4 Sulfur content of raffinate 1000 Jan -Sept 2002 / Oct Sept 2003 Lab ppm on line ppm Figure 26

28 ULSD ydrotreater DK 4 unit WABT in deg C Start to 10 ppm S catalyst life (t feed/ m³ catalyst) Figure 27

29 Refiner/reformer isomerization Jet fuel hydrotreating MD hydrotreating DESUS / FCC / Alkylation / ETBE ETBE Claus units Figure 28

30 FCC istory Catalyst Research Associates Agreement signed in London on 12 Oct 1938 Standard Oil of New Jersey (Esso) Standard Oil of Indiana (Amoco) Kellogg IG Farben added by Anglo-Iranian Oil (BP) Royal Dutch/Shell Texaco UOP Figure 29

31 FCC istory Group of 1000 Researchers Massachusetts Institute of Technology (W.K. Lewis and E. R. Gilliland) Big Research program (topped from Manhattan program only) 25 May 1942: Start up of first commercial Fluid Catalytic Cracking (FCC) Unit - Capacity t/yr - Location Baton Rouge refinery of Standard Oil of Louisiana Figure 30

32 Figure 31

33 early days of catalytic cracking synthetic catalyst era FCC Features at the Beginning and Today (1) catalysts highly temperature sensitive Reg.-temp. limited to 600 C residence time in regen min 0.6 % carbon on regenerated cat CO 2 /CO ratio 1 runaway afterburning 1000 C catalysts rel. low activity high recycle high coke yield today zeolitic catalyst era stable up to 800 C residence time in regen. 3-4 min < 0.05 % carbon on regen. cat complete combustion no afterburning high activity no recycle coke yield Figure 32

34 FCC Features at the Beginning and Today (2) early days of catalytic cracking Fluidized bed cracking - catalyst residence time sec - vapor residence time sec - Temperatur 500 C today Riser cracking - cat residence time 5-15 sec - vapor residence time 1-5 sec C Progress in Technology Equipment Catalyst Figure 33

35 FCC istory FCC Performance at the Begining and Today PCLA* No 1 May 1942 Today Feedstock Boiling range, C Catalyst natural day Cat/Oil 3.5 Cat losses kg/t 1.5 Reactor Temp. C 490 Conversion wt.-% 55 C 3 /C 4 wt.-% 10 Gasoline wt.-% Zeolite Re--Y ZSM * Powdered Catalyst Louisiana No.1 Figure 34

36 ... there have been so many changes in the... FCC unit that its forefathers wouldn t recognize their offspring. Figure 35

37 Cracking of VGO by FCC Flue gas Cracked products to Distillation Light Naphtha eavy Naphtha Regenerator Reactor Light Cycle Oil Slurry Air Vacuum Gasoil Figure 36

38 FCC Unit PCK Schwedt Figure 37

39 FCC Catalyst Additives - for low sulfur gasoline - for light olefines Figure 38

40 Possible Gasoline Sulphur Reduction Mechanisms A) Removal of S from gasoline precursors B) Removal of S from gasoline range molecules C) Conversion of heavy S species to coke Figure 39

41 FCC Catalyst Additives - for low sulfur gasoline - for light olefines Figure 40

42 70 World Propylene Demand by Region (source: G.McElhiney Grace) Asia Middle East East Europe West Europe South America North America Demand (million Metric Tons) World wide long term growth of 5-6 % per annum Figure 41

43 World-wide Propylene Production Use of ZSM-5 zeolite enables the FCC unit to make a valuable contribution to propylene production. This contribution is expected to increase significantly in the near future... Figure 42

44 European refiners must produce more diesel fuel reduce gasoline yield decrease production of heating oil. Figure 43

45 Fuels are becoming speciality chemicals (Ultimate, V-Power) there will be opportunities for new catalyst formulations to help control the composition of these products at a molecular level. Figure 44

46 Current catalyst market ( 13 billion $/yr) environmental catalysts 27 % polymers 22 % refining 21 % petrochemicals 20 % fine chemicals and inter mediates 10 % The refining catalyst market is the most competitive segment of the global catalyst market (bid contract basis). Figure 45

47 Sales of Refining Catalysts - world wide Billion $/yr growth rate 75 Million$/yr Figure 46

48 Capacities of catalytic units in Germany (Millions t/yr) Fluid Catalytic Cracking 18 ydrocracking 9 Catalytic Reforming 17 Alkylation 1 Isomerization 4 Ether 0.5 ydrotreating 87 (Naphtha 27/Kero 5/MD 43/VGO 12) Total % of crude capacity Figure 47

49 Catalysts in the Schwedt Refinery FCC ydrotreater Mild ydrocracker Isomerization Cat Reformer Ether (ETBE) Inventory Kilograms Annual Consumption kgs/yr Total Figure 48

50 rule of thumb added value by only 10 % performance improvement is much more than the total catalyst cost Figure 49

51 Potentials for Improvement deep hydrotreated FCC feed new FCC catalysts (Low -transfer) FCC Overcracking Reduction of gasoline acc. market Manufactoring of boosters (export) Increasement of propylene yield Increasement of biofuels (etherification of tertiary C 4 -/C 5+ -Olefines) Figure 50

52 FCC Yields (wt.-% on feed) Propylene Isobutane n-butanes Isobutene Isoamylenes (tert.) Naphtha Base Y-Zeolith + ZSM Overcracking (enhanced Catalyst) Figure 51

53 Closing Comments Needs both Teamplayers & Individuals Is of interest to both Academe + Industry R&D in catalysis will remain challenging and rewarding Figure 52

54 Thank you for your attention Figure 53