Hartmut Schütter · 2010. 5. 25. · DK 4 Advanced Control (RMPCT) 0 2 4 6 8 10 12 14 16 18 Feb.02 Mrz.02 Apr.02 Jun.02 Jul.02 Aug.02 Okt.02 Nov.02 Sulfur content of raffinate, ppm

Catalysis in a Refinery

Hartmut Schütter

x:15_Info_Vorträge_Ringvortrag Februar 2005

Figure 1

Boiling Range of Crude Oil (REB)

0100200300400500600700800900

0 20 40 60 80 100wt%

Boi

ling

Tem

pera

ture

°C

1,2% LPG

16% Naphtha

10% Kero

32% Diesel / HEL

appr. 50% atm. residue

33%Vacuumgasoils

17%Vacuum-residue

(Heavy Fueloil/Bitumen)


Figure 2

Crude Oil Distillation

Crude Oil

Vacuum residue(Bitumn/Heavy Fuel Oil

VGO Hydrotreater/Cat Cracker

Gas/ LPG

Hydrotreater(Diesel/Domestic FuelOil)Hydrotreater(Jet Fuel)Cat Reformer(Gasoloine Pool)Cat Reformer(Aromatics)Steam CrackerIsomerization(Gasoline Pool)

Middledistillates

Mid/Heavy Naphtha

Light NaphthasSteamreformer(H2)FuelSteam Cracker

atm.Distillation

Vacuumdistillation


Figure 3

Demand of Oil Products differs from Composition of Crude Oil

050

100150200250300350400450500550600650700

0 10 20 30 40 50 60 70 80 90 100

Percentage wt%

Boi

ling

Tem

pera

ture

°C

Refining

Technical Services PCK

crude oilR ussian E xport B lend

32.4 °API 1.5 %S

market demand


Figure 4

CrudeOil

RefineryTargetYields

1.2

5

16

30

32

55

50

5

NaphthaRON500ppm

GasolineRON92 -100

S 3%

Heavy Fuel Oil S


Figure 5

DESUS / FCC /Alkylation / ETBE

Refiner/reformerisomerization

Jet fuelhydrotreating

MD hydrotreating

Claus units

ETBE


Figure 6

Gasoline Upgrading

• Increasement of Octane number by IsomerizationConversion of normal C5/C6 Paraffins to iso Paraffins

• Increasement of Octane number by catalytic ReformingAromatics from Dehydrogenation of Naphthenes as well as Dehydrocyclisation of Paraffins

• Increasement of Octane number by AlkylationConversion of iso C4 with Butenes to iso Octane

• Increasement of Octane number by EtherificationConversion of iso Butene with Ethanol to ETBE


Figure 7

l Antiknock Property– Octane number = 0

100 Vol% n-Heptane

– Octane number = 100100 Vol% iso-Octane

Octane number

HHHHHHH|||||||

HCCCCCCCH|||||||

HHHHHHH

−−−−−−−−

HHHH|

H-C-HH

|||||HCCCCCH

|||||

HH-C-H

|H

HH-C-H

|H

H

−−−−−−


Figure 8

Light Naphtha Isomerization


Figure 9

Catalytic Reforming


Figure 10

Ether


Figure 11




MD hydrotreating

Claus units

ETBE


Figure 12

Development of Sulfur Limit in Gasoline

500

150

5010

050

100150200250300350400450500

Sulf

ur

in p

pm

bis 2000 2000 2001 2002


Figure 13

Development of Sulfur Limit in Diesel Fuels

10000

5000

50050 10

0100020003000400050006000700080009000

10000Su

lfur i

n pp

m

past 80/90 1995 2000 2002


Figure 14

Diesel Hydrotreating


Figure 15

Increasing of Desulfurization from 95 % up to more than 99.9 %with existing Hydrotreaters by increasing of Reactortemperature only ?

⇒ > + 40 ° C WABT⇒ Reactor outlet temperature > 400 °C

▪ material?▪ Cycle length ↓ ↓ ↓▪ Productstability (color, ox.stab.)▪ target sulfur critical (10 ... 20 ppm → recombination to RSH,

Thiophene)


Figure 16

AOP - Targets

l Reliability

l Flexibility

l Potential to future

l Low opex (not lowest investment)

l Improved margin


Figure 17

Hydrogen partial pressure in the reactor

40

42

44

46

48

50

52

54

56

0 20 40 60 80 100

pH2,ba

r

Recycle gas ratio 250 Nm³/m³∆p Reactor 2 bar

PH2S=1,86bar

> 50% higher reaction rate constant

Recycle gas ratio 150 Nm³/m³∆p Reactor 4 bar

PH2S=3,92bar

catalyst bed length relativ, %


Figure 18

Basic desulfurization reactions

sulfides > thiophenes > benzothiophenes > dibenzothiophenes


Figure 19

HDS - Kinetic

−⋅

−= −− 1

01

111 nn SSn

LHSVk

95,0% HDS → LHSV = 1·x99,9% HDS → LHSV = 0.33·x

⇒ Cat requirement 3 times more


Figure 20

DK 4

R2weight 535 tda = 4.6 ms = 98 mmh = 43.5 m


Figure 21

DK4 Reactors R-901 and R-902

R-901

R-902

60.03 bar325 °C

357 °C

Quenchgas

7.1 weight ppm S

382 m³/h329 t/h

352 °C

363 °C

361 °C 361 °C 360 °C

∆p=0.56 bar

325 °C 325 °C 326 °C

338 °C 338 °C 339 °C

338 °C 338 °C 340 °C

354 °C 353 °C 352 °C

356 °C 357 °C 357 °C

352 °C353 °C352 °C

356 °C 357 °C 358 °C

360 °C 360 °C 360 °C

362 °C363 °C361 °C

56.85 kNm³/h

∆p=0.26 bar

∆T (R-901)=33 K ∆T (R-902)=11 K

WABT (R-901 & R-902)=350°C

23.09.2003 13:30:13


Figure 22

DK 4 Reactor – pressure drop

0.00.20.40.60.81.01.21.41.61.82.02.22.42.6

Jan-0

1

Apr-0

1Ju

l-01

Nov-0

1

Feb-0

2

May-0

2

Sep-0

2

Dec-0

2

Mar-0

3

Jun-0

3

Oct-0

3

pres

sure

dro

p o

f R 9

01 +

R 9

02 (b

ar)

Technical Services PCK

0.2 bar per 30 months < < 0.01 bar per month


Figure 23

R M P C T - DK4(Robust Multivariable Predictive Control Technology) controlerstatus: ON

03.12.2002 10:02:46

321°C

actual vorausber.

321°C

385 t/h 385 t/h MV is ONStatus

MV is ON

min. max.365 t/h

316°C

385 t/h

362°C

1 bar402°C643°C71%365°C1057 A6.81 ppm

aktuell Status

1 bar

vorausber.

403°C644°C71%364°C1059 A7,20 ppm

GOODGOODGOODGOODGOODGOODGOOD

1 bar0°C0°C10%0°C0 A0,00 ppm

6 bar460°C700°C95%380°C1230 A7,20 ppm

min. max.

Set points (Sollwerte): Feed heater outlet temperature O-901

FC9011:

TC9027:

Monitored points:

pressure Feed – control valve FC9011 Max. Skintemperature O-901

Max. combustion chambertemperature O-901Opening control valve fuelgas to O-901 Max. ReactortemperatureAmpere V-901 Raffinate sulfur

Comparison measurement/calculated: Suflur analyzed: Sulfur calculated (corr.): 6.81 ppm

6.37 ppmSulfur caculated (uncorr):

6.82 ppm


Figure 24

DK 4 Advanced Control (RMPCT)

02

46

810

1214

1618

Feb.02 Mrz.02 Apr.02 Jun.02 Jul.02 Aug.02 Okt.02 Nov.02

Sul

fur

cont

ent o

f raf

finat

e, p

pm

actual data

Set points


Figure 25

Changeover fuel quality from 50 to < 10 ppm Sulfur

1

10

100

0 20 40 60 80 100 120

Su

lfu

r co

nte

nt,

pp

m

Supply 9 ppm

Supply 4 ppm

days


Figure 26

DK 4 Sulfur content of raffinate

1

10

100

1000

1 10 100 1000

on line ppm

Lab

ppm

Jan -Sept 2002 / Oct 2002 - Sept 2003


Figure 27

ULSD Hydrotreater DK 4 unit

300310320330340350360370380390400

0 1000 2000 3000 4000 5000 6000 7000 8000 9000catalyst life (t feed/ m³ catalyst)

WA

BT

in d

eg C

Start to 10 ppm S


Figure 28




MD hydrotreating

Claus units

ETBE


Figure 29

FCC HistoryCatalyst 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 30

FCC HistoryGroup 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 commercialFluid Catalytic Cracking (FCC) Unit

- Capacity 500 000 t/yr

- Location Baton Rouge refinery of Standard Oil of Louisiana


Figure 31


Figure 32

FCC Features at the Beginningand Today (1)

• 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

• synthetic catalyst era• catalysts highly temperaturesensitive → Reg.-temp. limitedto 600 °C ⇒ residence time in regen. 10 -15 min⇒ 0.6 % carbon on regenerated cat⇒ CO2/CO ratio ∼ 1⇒ runaway afterburning

→ 1000 °C• catalysts rel. low activity

→ high recycle→ high coke yield

todayearly daysofcatalytic cracking


Figure 33

FCC Features at the Beginningand Today (2)

todayearly daysofcatalytic cracking

• Riser cracking- cat residence time 5 - 15 sec- vapor residence time 1 - 5 sec- 540 °C

• Fluidized bed cracking- catalyst residence time 30 -120 sec- vapor residence time 10 - 60 sec- Temperatur 500 °C

⇒ Progress in TechnologyEquipmentCatalyst


Figure 34

FCC History

360 - 560

Zeolite Re-H-Y ZSM 57.5

0.15540802448

FeedstockBoiling range, °C 265 - 400

Catalyst natural dayCat/Oil 3.5Cat losses kg/t 1.5Reactor Temp. °C 490Conversion wt.-% 55C3/C4 wt.-% 10Gasoline wt.-% 38

TodayPCLA* No 1 May 1942

FCC Performance at the Begining and Today

* Powdered Catalyst Louisiana No.1


Figure 35

... there have been so many changes

in the ... FCC unit that its forefathers

wouldn‘t recognize their offspring.


Figure 36

ReactorRegenerator

Air

Vacuum Gasoil

Flue gasCracked products to Distillation

Light Naphtha

Light Cycle Oil

Slurry

Heavy Naphtha

Cracking of VGO by FCC


Figure 37

FCC Unit PCK Schwedt


Figure 38

FCC Catalyst Additives

- for low sulfur gasoline

- for light olefines


Figure 39

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 40

FCC Catalyst Additives

- for low sulfur gasoline

- for light olefines


Figure 41

0

10

20

30

40

50

60

70

1993

1994

1995

1996

1997

1998

1999

2000

2001

2002

2003

Dem

and

(mill

ion

Met

ric T

ons)

Asia Middle East East Europe West Europe South America North America

World Propylene Demand by Region(source: G.McElhiney Grace)

• World wide long term growth of 5-6 % per annum


Figure 42

Ø Use of ZSM-5 zeolite enables the FCC unitto make a valuable contribution

to propylene production.

Ø This contribution is expectedto increase significantly in the near future...

World-wide Propylene Production


Figure 43

European refiners must

produce more diesel fuel

reduce gasoline yield

decrease production of heating oil.


Figure 44

Fuels are becomingspeciality 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 45

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 46

Sales of Refining Catalysts- world wide -

∼ 2.5 Billion $/yr

growth rate 75 Million$/yr


Figure 47

Capacities of catalytic unitsin Germany (Millions t/yr)

Fluid Catalytic Cracking 18

Hydrocracking 9

Catalytic Reforming 17

Alkylation 1

Isomerization 4

Ether 0.5

Hydrotreating 87(Naphtha 27/Kero 5/MD 43/VGO 12)__________________________________________

Total 136.5⇒ ≈ 120 % of crude capacity


Figure 48

Catalysts in the Schwedt Refinery

1 460 0002 220 000Total

1 000 000400 00030 00010 00010 00010 000

200 0001 700 000

65 00090 000

105 00060 000

FCCHydrotreaterMild HydrocrackerIsomerizationCat ReformerEther (ETBE)

AnnualConsumption

kgs/yr

InventoryKilograms


Figure 49

rule of thumb

added value by only 10 %

performance improvement

is much more than the

total catalyst cost


Figure 50

Potentials for Improvement

l deep hydrotreated FCC feed

l new FCC catalysts (Low H-transfer)FCC Overcracking

Reduction of gasoline acc. market

Manufactoring of boosters (export)

Increasement of propylene yield

Increasement of biofuels(etherification of tertiary C4-/C5+-Olefines)


Figure 51

FCC Yields (wt.-% on feed)

13.0

8.8

9.3

3.9

3.1

26.9

7.0

4.7

5.2

2.1

1.7

45.7

Propylene

Isobutane

n-Butanes

Isobutene

Isoamylenes (tert.)

Naphtha

Overcracking(enhanced Catalyst)

BaseY-Zeolith + ZSM5


Figure 52

• Needs bothTeamplayers & Individuals

• Is of interest to bothAcademe + Industry

Closing Comments

• R&D in catalysis will remainchallenging and rewarding


Figure 53

Thank you for your attention

Documents

Hartmut Schütter · 2010. 5. 25. · DK 4 Advanced Control (RMPCT) 0 2 4 6 8 10 12 14 16 18 Feb.02 Mrz.02 Apr.02 Jun.02 Jul.02 Aug.02 Okt.02 Nov.02 Sulfur content of raffinate, ppm