Fall 2003

Hydrocarbon Processes in the Oil Refinery Prof. Dr. J.A. Moulijn dr.ir. M. Makkee

Industrial Catalysis
DelftChemTech Delft University of Technology The Netherlands

http://www.dct.tudelft.nl/race

Hydrocarbon processes in the Oil Refinery Content Lectures

Chemical Process Technology, Wiley, 2001
J. A. Moulijn, M. Makkee, A.E. van Diepen Chapter 2, Crude oil compositions (2.3.3) Chapter 3, Processes in the Oil Refinery Chapter 5, Synthesis Gas (5.1, 5.2, and 5.4) Chapter 6, Fischer Tropsch (6.3)

Lecturing notes - Speakers from Industry

CARE, Chemical Process Technology TUDelft lectures background knowledge

&CE

Programme
Up to 29 September 30 September 6 October 7 October 13 October 14 October

Lectures Moulijn/Makkee Dr. H.P.A. Calis (Shell)

Fischer Tropsch

ir. A. Rooijmans (ExxonMobil)

Flexicoking

dr. F. Plantenga (Akzo-Nobel)

Hydrotreating + Alkylation

ir. H. van Wechem (Shell)

Upgrading Shell Pernis Refinery (Per+)

Dr. R. Antonelli (UOP)

Trends for the future Refinery

TUDelft

&CE

Oil refinery; an overview

TUDelft

&CE

Introduction
Chapter 2
Composition crude oil

Chapter 3
Refinery Relatively mature optimised plants
Nevertheless changes Market Legislation

Some 600 worldwide Large volumes Very instructive example chemical process technology

TUDelft

&CE

Modern oil refinery

LPG and Gas LPG Straight run gasoline Atmospheric Distillation LPG Naphtha Middle distillates Heavy atm. gas oil Vacuum gas oil Solvent extraction Lube base stocks Hydrotreating Catalytic reforming Reformate Gasoline Hydrotreating Hydrotreating Cycle oil Hydrocracking Gasoline, Naphtha, Middle distillates Solvent dewaxing LPG and Gas Gasoline, Naphtha, Middle distillates Visbreaker Delayed coker / Flexicoker Fuel oil Asphalt Gasoline, Naphtha, Middle distillates Industrial fuels Coke Lube oils Waxes Catalytic cracking Gasoline Slurry oil Treating and Blending Solvents Kerosene Diesel Heating oil Lube oil Greases Asphalt Alkylation Alkylate Refinery fuel gas

Crude oil

Vacuum Distillation

Propane deasphalter

TUDelft

&CE

Distillation Fractions
Distillate fraction Gases Gasoline Naphtha Kerosine (jet fuel) Diesel, Fuel oil Atmospheric Gasoil Heavy Fuel Oil Atmospheric Residue Vacuum Residue Boiling point C-atoms/ molecule (oC) <30 30-210 100-200 150-250 160-400 220-345 315-540 >540 >615 1-4 5-12 8-12 11-13 13-17

Middle Destillates

20-45 >30 >60

TUDelft

&CE

Processes in an Oil Refinery

Physical processes Distillation Solvent extraction Propane deasphalting Solvent dewaxing Blending Chemical processes Thermal Catalytic Visbreaking Delayed coking Flexicoking Hydrotreating Catalytic reforming Catalytic cracking Hydrocracking Catalytic dewaxing Alkylation Polymerization Isomerization R

TUDelft

&CE

Physical Processes

TUDelft

&CE

Simple Crude Distillation

Gases

C1 - C4
reflux water

Gasoline

620 K
steam

steam steam

Kerosene

Gas oil Crude oil Furnace Fractionator Stripper Stripper Residue

TUDelft

&CE

Market Demands
Clean products (no S, N, O, metals, etc.) More gasoline (high octane number) More diesel (high cetane number) Specific products (Aromatics, alkenes, etc.) Less residue

How to meet these demands?

More sophisticated distillation Physical separation steps Chemical conversion steps

TUDelft

&CE

More sophisticated ??? Higher T distillation ??

Gases

C1 - C4
reflux water

Gasoline

620 K
steam

steam steam

Kerosene

Gas oil Crude oil Residue Furnace Fractionator Stripper Stripper

TUDelft

&CE

Modern Crude Distillation Unit

Crude Oil

Gases

reflux

water

Gasoline

circulating reflux vacuum

Slops

circulating reflux steam

vacuum

Intermediate gas oil

vacuum residue

Heavy gas oil Kerosene

steam

Light gas oil Strippers Furnace Mild vacuum column Driers

Furnace

TUDelft

Main fractionator

&CE

Modern oil refinery

LPG and Gas LPG Straight run gasoline Atmospheric Distillation LPG Naphtha Middle distillates Heavy atm. gas oil Vacuum gas oil Solvent extraction Lube base stocks Hydrotreating Catalytic reforming Reformate Gasoline Hydrotreating Hydrotreating Cycle oil Hydrocracking Gasoline, Naphtha, Middle distillates Solvent dewaxing LPG and Gas Gasoline, Naphtha, Middle distillates Visbreaker Delayed coker / Flexicoker Fuel oil Asphalt Gasoline, Naphtha, Middle distillates Industrial fuels Coke Lube oils Waxes Catalytic cracking Gasoline Slurry oil Treating and Blending Solvents Kerosene Diesel Heating oil Lube oil Greases Asphalt Alkylation Alkylate Refinery fuel gas

Crude oil

Vacuum Distillation

Propane deasphalter

TUDelft

&CE

Propane Deasphalting Extraction

Reason Coke-forming tendencies of asphaltenic materials How? Reduction by extraction with suitable solvent
propane butane, pentane

Why propane?
Easy separation Available ...

Conditions?
Modest temperature High pressure

Flow scheme?

TUDelft

&CE

Propane Deasphalting
Condensers Propane recycle Steam Steam condenser

Vacuum residue

Propane evaporator
310 - 330 K 35 - 40 bar

Cond.

Water

Steam

Make-up propane

Deasphalted oil

Liquid propane

Steam

Asphalt Propane storage Deasphalting tower Flash drum Strippers

TUDelft

&CE

Modern oil refinery

LPG and Gas LPG Straight run gasoline Atmospheric Distillation LPG Naphtha Middle distillates Heavy atm. gas oil Vacuum gas oil Solvent extraction Lube base stocks Hydrotreating Catalytic reforming Reformate Gasoline Hydrotreating Hydrotreating Cycle oil Hydrocracking Gasoline, Naphtha, Middle distillates Solvent dewaxing LPG and Gas Gasoline, Naphtha, Middle distillates Visbreaker Delayed coker / Flexicoker Fuel oil Asphalt Gasoline, Naphtha, Middle distillates Industrial fuels Coke Lube oils Waxes Catalytic cracking Gasoline Slurry oil Treating and Blending Solvents Kerosene Diesel Heating oil Lube oil Greases Asphalt Alkylation Alkylate Refinery fuel gas

Crude oil

Vacuum Distillation

Propane deasphalter

TUDelft

&CE

Thermal Processes

TUDelft

&CE

Thermal Processes
gas Feed
Furnace T, tres Visbreaking mild conditions

oil coke
Delayed Coking long residence time (24 h)

Flexicoking combination thermal cracking and coke gasification/combustion Steam Cracking production lower olefins TUDelft

&CE

Thermal Processes
VISBREAKING
Mild thermal cracking Reduction of viscosity

DELAYED COKING
Long residence times (24 h) Heavy feed coke + oil + gas

FLEXICOKING
Combination of thermal cracking and coke gasification / combustion

TUDelft

&CE

Visbreaking
Gasoline ~ 10 wt% Heavy gas oil

Vacuum residue

730 K 20 bar

~ 80 wt% Cracked residue

Light gas oil

Furnace

Reactor

Flash

Fractionator

Vacuum fractionator

TUDelft

&CE

Delayed Coking
Gas
710 K

Unstabilized Naphtha
2 bar

770 K

Gas oil Coke Coke drums Furnace Fractionator Gas oil stripper

Feed

TUDelft

&CE

Catalytic Processes

TUDelft

&CE

Market Demands
Clean products (no S, N, O, metals, etc.) More gasoline (high octane number) More diesel (high cetane number) Specific products (Aromatics, alkenes, etc.) Less residue

How to meet these demands?

More sophisticated distillation Physical separation steps Chemical conversion steps

TUDelft

&CE

Octane Numbers, Boiling Points

n-pentane 2-methyl butane cyclopentane n-hexane 2,2-dimethylbutane benzene cyclohexane n-octane 2,2,3-trimethylpentane methyl-tertiary-butyl-ether straight run gasoline FCC light gasoline alkylate reformate (CCR) 62 90 85 26 93 >100 77 0 100 118 68 93 95 99 309 K 301 322 342 323 353 354 399 372 328 67 (MON) 82 92 88

TUDelft

&CE

Cetane Numbers
TUDelft n-alkanes n-hexadecane (cetane) iso-alkanes alkenes cycloalkanes alkylbenzenes naphtalenes -methyl naphtalene straight run gas oil FCC cycle oil thermal gas oil hydrocracking gas oil 100-110 100 30-70 40-60 40-70 20-60 0-20 0 40-50 0-25 30-50 55-60 R

&CE

Fluid Catalytic Cracking (FCC)

TUDelft

&CE

Catalytic Cracking
World capacity: > 500 million metric ton/year
CH3 H3C C + CH3 CH2 C CH3 CH3 CH3 H3C C CH2 + + C CH3 CH3 CH3

scission

Reactions:
C-C bond cleavage: Isomerization Protonation/deprotonation Alkylation Polymerization Cyclization, condensation

coke formation

TUDelft

&CE

Cracking Mechanism
Alkenes: via carbenium ions
R CH C H2 + H+

H R C H2 C + H
or

C+ H

C H3

Stability: tertiary > secondary > primary > ethyl > methyl
Alkanes: via carbonium ions
H
R C H2 C H3

+ H+

C+ H H

C H3

C+ H

C H3

+ H2

Or, if carbenium ions are present:

H 3C

C H

C H2 C H2 C H2 C H3
+

H 3C
H 3C

C H

C H2 C H2 C H2 C H3 +
C H2 C H2 C H3

H 3C

C+ C H3

C H2 C H2 C H3

CH C H3

TUDelft

&CE

Mechanism of cracking of alkanes

H3C CH2 CH2 CH2 CH2 CH2 CH3
Initation

n-Alkane

H3C CH CH2 CH2 CH2 CH2 CH3

Classical carbenium ion

H3C CH CH CH2 CH2 CH3 H+ CH2

Protonated cyclopropane
Isomerization

hydride shifts + C-C bond breaking

H3C CH CH3 + H2C CH CH3 CH3

hydride transfer

H3C CH CH CH2 CH2 CH3 CH3

etc.

n-Alkene

H3C CH CH3 CH3

iso-Alkane

Count the Hs! What is wrong??

TUDelft

&CE

Product Distribution Thermal versus Catalytic Cracking

140

mol per 100 mol cracked n-C16

Thermal
120 100 80 60 40 20 0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

Catalytic

Carbon Number

TUDelft

&CE

Modern oil refinery

LPG and Gas LPG Straight run gasoline Atmospheric Distillation LPG Naphtha Middle distillates Heavy atm. gas oil Vacuum gas oil Solvent extraction Lube base stocks Hydrotreating Catalytic reforming Reformate Gasoline Hydrotreating Hydrotreating Cycle oil Hydrocracking Gasoline, Naphtha, Middle distillates Solvent dewaxing LPG and Gas Gasoline, Naphtha, Middle distillates Visbreaker Delayed coker / Flexicoker Fuel oil Asphalt Gasoline, Naphtha, Middle distillates Industrial fuels Coke Lube oils Waxes Catalytic cracking Gasoline Slurry oil Treating and Blending Solvents Kerosene Diesel Heating oil Lube oil Greases Asphalt Alkylation Alkylate Refinery fuel gas

Crude oil

Vacuum Distillation

Propane deasphalter

TUDelft

&CE

Catalysts for FCC

Mechanism: H+ donor or H- acceptor acid sites
Originally AlCl3 solution: corrosion waste streams Subsequently Clays (acid-treated) Amorphous silica-alumina more stable and more selective better pore structure better attrition stability Zeolites even more active and stable less coke, higher thermal stability

TUDelft

&CE

Cracking Catalysts
silica: Si O Si O Si OH O Si silica-alumina: Si O Si O Al HO Si O Si Si O O Si Si O Si O

H+

Weak acid
Si O O Si

+ H+

Si O Al O Si

Strong acid TUDelft R

&CE

Zeolites
Large number found and/or synthesized Total porosity up to 0.5 ml/g Examples
Supercage 0.8 nm Sodalite cage

Sodalite

SOD

FAU

Y (Faujasite) Zeolite A
LTA

TUDelft

&CE

FCC process
Catalyst zeolite
Small pores Particle size?? Reactor?

Product distribution
Broad mixture, including coke

Thermodynamics
Exothermal, endothermal? Temperature?, pressure?

TUDelft

&CE

Production of FCC catalyst

RECl3, NH4Cl Wash liquor Sodium silicate Sodium aluminate Water NaOH

Micro pores Meso pores Macro pores

< 3 nm 3 - 50 nm > 50 nm
zeolite matrix (dp = 2-10 m)

Ion exchange Na zeolite Filter crystallization Dryer

Zeolite

50-70 m

Al2O3 source SiO2 source Water NaOH Matrix material FCC catalyst particles

Silica-alumina synthesis

Mixer

Spray dryer

TUDelft

&CE

Product Distribution of Gas Oil Cracking

100 Gas LPG 80

Coke
Carbon deposited Catalyst poisoned on s scale

% wt on feed

60

Gasoline

40 LCO 20 HCO/slurry 0 1950s 1960s 1970s REY 1980s Zeolite USY Amorphous Low Al High Al Coke

Process Design? Coke R CE Mixed Blessing

TUDelft

Regeneration by coke combustion provides heat

&

FCC: Fluidized-bed Reactor and Regenerator

C + O2 CO / CO2
Flue gas

To fractionation
2-stage Cyclones 775 K Fluidized bed

Cracking

2-stage Cyclones 970 K Fluidized bed Grid

Steam Spent catalyst Riser

Later much more active catalyst Consequences for process?

Air

Feed

Regenerated catalyst

Regenerator

Reactor

TUDelft

Pros and cons fluid beds??

&CE

Modern FCC Unit: Riser Reactor

G/L sep. cyclones gas (C2 and lighter) propane propene

flue gas

waste heat boiler

catalyst fines

L/L sep. spent cat. regenerated cat. water steam riser light cycle oil heavy cycle oil slurry oil steam

expansion Air compression

butane

Feed

Gasoline Absorber Debutanizer

butene

Regenerator

Reactor

Fractionator

Depropanizer

TUDelft

&CE

Typical Conditions in Riser FCC

Reactor Temperature (K) Pressure (bar) Residence time 775 1 1-5 s

Regenerator 973 2 minutes/half hour

TUDelft

&CE

Riser Reactor: Plug flow Reactor?? Residence Time Distribution ?

Catalyst fraction (a.u)

Total area = 1

0 Time (s)

20

TUDelft

&CE

Catalytic Cracking Capacity in the US

Feed throughput (million barrels/day)
7

6.5

Capacity required with amorphous catalysts (extrapolated)

5.5

Capacity with zeolitic catalysts (actual situation)

4.5 1960 1965 1970 1975 1980 1985 1990 1995

Year

TUDelft

&CE

Sulfur Distribution in FCC Products

Capacity: catalyst / oil ratio: Catalyst inventory: Catalyst recirculation rate: feedstock sulfur content: 50000 barrels /day 6 kg/kg 500 ton 50000 ton/day 2 wt%

product H2S Liquids Coke

% of sulfur in ton S/day feed 50 84 43 7 72 12

TUDelft

Do we have a problem?

&CE

Effect of HDS of FCC feedstock on gasoline sulfur content

FCC gasoline sulfur, ppmw

10000

1000 untreated feed 100

10

1 0 0.5 1 1.5 2

FCC feedstock sulfur, wt.%

TUDelft

&CE

How to avoid SO2 emission FCC unit without capital investment???

Trapping SO2 in regenerator by the formation of sulfate

2 SO2 + O2 2 SO3 SO3 + MO MSO4

What happens in the riser?? Dependent on the metal the sulfate is not stable in riser (or stripper)

MSO4 + H2 MSO3 + H2O H2

MO + H2S or MS + H2O H2 O

Sulfates of Ce, Mg,.. TUDelft

Stable in regenerator Not in riser

MO R

&CE

Novel Developments in FCC

0.51 - 0.55 nm

Production of light alkenes (C3=, C4=)

addition of ZSM-5 application petrochemical feedstock isobutene for MTBE, ETBE

Processing of heavier feedstocks

improved reactors, strippers, feed injection, gas/solid separation application of catalyst cooling and high T much higher coke production, metal deposits, more sulfur

TUDelft

&CE

Hydroprocessing

TUDelft

&CE

Modern oil refinery

LPG and Gas LPG Straight run gasoline Atmospheric Distillation LPG Naphtha Middle distillates Heavy atm. gas oil Vacuum gas oil Solvent extraction Lube base stocks Hydrotreating Catalytic reforming Reformate Gasoline Hydrotreating Hydrotreating Cycle oil Hydrocracking Gasoline, Naphtha, Middle distillates Solvent dewaxing LPG and Gas Gasoline, Naphtha, Middle distillates Visbreaker Delayed coker / Flexicoker Fuel oil Asphalt Gasoline, Naphtha, Middle distillates Industrial fuels Coke Lube oils Waxes Catalytic cracking Gasoline Slurry oil Treating and Blending Solvents Kerosene Diesel Heating oil Lube oil Greases Asphalt Alkylation Alkylate Refinery fuel gas

Crude oil

Vacuum Distillation

Propane deasphalter

TUDelft

&CE

Hydrotreating and Hydrocracking

HYDROTREATING Conversion with hydrogen Reactions: hydrogenation & hydrogenolysis Removal of hetero-atoms (S, N, O) Some hydrogenation of double bonds & aromatic rings Molecular size not drastically altered Also termed hydropurification HYDROCRACKING Similar to hydrotreating Drastic reduction in molecular size

TUDelft

&CE

Hydrotreating

TUDelft

&CE

Why Hydrotreating ?
Protection of the environment
reduction acid rain

Protection of downstream catalysts

in further processing S-compounds in Diesel fuel give difficulties in catalytic cleaning of exhaust gases

Improvement of gasoline properties

odour, colour, stability, corrosion

TUDelft

&CE

Hydrotreating Reactions
1) Mercaptans RSH + H2 RH + H2S

HDS
H2S

2) Thiophenes S 3) Benzothiophenes S 4) Pyridines N OH 5) Phenols

+ 3 H2

HDS

+ 5 H2

+ H2S

HDS

+ 5 H2

NH3

HDN

H2

H2O

HDO

TUDelft

&CE

Equilibrium data
100 90 80 70 60 S

lnKeq

Industrial conditions 600-650 K

50 40 30 20 10 0 0 1 2 3 4 5 CH3SH

1000/Temperature (1/K)

TUDelft

&CE

Typical process conditions

I I I I

Naphtha Temperature (K) 590 - 650 Pressure (bar) 15 - 40 H2/oil (Nm3/kg) 0.1 - 0.3 WHSV (kg feed/(m3 catalyst)/h) 2000 - 5000
I

Gas Oil 600 - 670 40 - 100 0.15 - 0.3 500 - 3000

Catalyst: mixed metal sulfides (CoS and MoS2 or NiS and WS2 on Al2O3) CoMoS
Co S Mo -Al2O3

TUDelft

Process design ???

&CE

Trickle-bed Reactor
Gas + liquid

Gas Liquid

Deflector Distributor Inert beads Catalyst bed Incomplete wetting Support grid Catalyst particle with liquid film Product Gas Complete wetting

TUDelft

&CE

Hydrotreating Process (trickle bed)

H2S hydrogen recycle to H2S removal Gas (C3-) Cold HP separator

Hydrogen

Recycle gas scrubbing

water

Naphtha

Sour water

steam

Product Feed Furnace Reactor Hot HP separator Hot LP separator Stripper Separator

TUDelft

&CE

Development of maximum Sulfur Content in automotive Diesel in Europe

3500

3000

3000

2500

2000

1500

Max S in Diesel ppm

500
1 2

1000

500

350 50
3

< 1996

TUDelft

1996 2000 Year

2005

&CE

Activity of Various Catalysts for HDS of Pretreated Gas Oil

S
CH3

S
CH3 CH3

S
C2H5

CH3

Feed

760 ppm

CoMo/-Al2O3

260 ppm

What catalyst do you select for Naphta Heavy gasoil

NiMo/-Al2O3

230 ppm

???

NiW/-Al2O3

200 ppm

Deep desulphiding

Pt/ASA

140 ppm

??? R

PtPd/ASA (I)

60 ppm

TUDelft

Retention time

&CE

Hydrocracking

TUDelft

&CE

Hydrocracking
Similar to FCC

but H2 inhibits some secondary reactions

e.g. coke formation

Catalyst ???
Ni

NiMoS

S Mo

Acid sites
SiO2, Al2O3, silica-alumina, zeolites

Silica-alumina

Hydrogenation sites
NiS/MoS, NiS/WS2, Pt NH3 inhibits reaction H2S inhibits reaction

TUDelft

&CE

Reactions during Hydrocracking

H0208 (kJ/mol)
Hetero-atom removal N H Aromatics hydrogenation + 2 H2 + 3 H2 + 6 H2 + NH3

- 374 - 326 - 119 - 44 -4

Hydrodecyclization

+ 3 H2

Alkanes hydrocracking

+ H2

Hydro-isomerization

TUDelft

&CE

Process Configurations for Hydrocracking

Gas Naphtha MD Gas Naphtha MD

Feed

HT/HC

Feed
Hydrowax

HT

HC

Single stage / once through

Two stage

low investment inhibition

Feed

Gas Naphtha MD

high investment high rates

HT = hydrotreating HC = hydrocracking MD = middle distillates

HT

HC

TUDelft

Series flow

&CE

Two-stage Hydrocracker
Fresh hydrogen Hydrogen recycle Purge to acid gas and NH3 removal
Quench H2 Quench H2

C1 C4

Naphtha Middle distillates

Feed Furnace Reactor Furnace Reactor High/Low pressure Fractionator separators

TUDelft

&CE

Summary of Processing Conditions

Mild Temperature (K) Hydrogen pressure (bar) Total pressure (bar) Catalyst 670 700 50 80 70 100 Ni/Mo/S/-Al2O3 +P*

single stage / first stage 610 710 80 130 100 150 Ni/Mo/S/-Al2O3 +P*

second stage 530 650 80 130 100 150 Ni/W/S/USY zeolite

TUDelft

&CE

Modern oil refinery

LPG and Gas LPG Straight run gasoline Atmospheric Distillation LPG Naphtha Middle distillates Heavy atm. gas oil Vacuum gas oil Solvent extraction Lube base stocks Hydrotreating Catalytic reforming Reformate Gasoline Hydrotreating Hydrotreating Cycle oil Hydrocracking Gasoline, Naphtha, Middle distillates Solvent dewaxing LPG and Gas Gasoline, Naphtha, Middle distillates Visbreaker Delayed coker / Flexicoker Fuel oil Asphalt Gasoline, Naphtha, Middle distillates Industrial fuels Coke Lube oils Waxes Catalytic cracking Gasoline Slurry oil Treating and Blending Solvents Kerosene Diesel Heating oil Lube oil Greases Asphalt Alkylation Alkylate Refinery fuel gas

Crude oil

Vacuum Distillation

Propane deasphalter

TUDelft

&CE

Catalytic Reforming

TUDelft

&CE

Catalytic Reforming
Important for gasoline production
Increases octane number

Important for base chemicals production

aromatics H2

TUDelft

&CE

Octane Numbers, Boiling Points

n-pentane 2-methyl butane cyclopentane n-hexane 2,2-dimethylbutane benzene cyclohexane n-octane 2,2,3-trimethylpentane methyl-tertiary-butyl-ether straight run gasoline FCC light gasoline alkylate reformate (CCR) 62 90 85 26 93 >100 77 0 100 118 68 93 95 99 309 K 301 322 342 323 353 354 399 372 328 67 (MON) 82 92 88

TUDelft

What reactions would you carry out??

&CE

Reactions for Increase of Octane Number

H0208 (kJ/mol) Isomerization
C C C C C C C C C C C C C C

-4

26
Cyclization
C C C C C C C

73
C

+ H2

+ 33 + 205

~ 50
Aromatization
C C

+ 3 H2

~ 40
Combination
C C C

~ 100
C

+ 3 H2

+ 177

Octane number

TUDelft

&CE

Aromatization of Cyclohexane Effect of T and p

1 0.9

Cyclohexane conversion (-)

0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 500 550 600 650 700 750 800

1 bar

5 bar 10 bar

25 bar

Favourable
low pressure high temperature

Temperature (K)

TUDelft

&CE

Aromatization of Cyclohexane Effect of T and H2/CH feed ratio

1 0.9

Cyclohexane conversion (-)

0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 500 550 600 650 700 750 800

0 5 10 H2/cyclohexane (mol/mol)

Temperature (K)

TUDelft

&CE

Conceptual process design?

Thermodynamics

high T low p H >>0

Catalyst stability highest for

low T excess H2 low S impurity removal coke by combustion restoring acidity by Cl2 treatment Redispersion of noble metal

Catalyst regeneration possible

Time scale stability dependent on conditions months days How to handle deactivation?? Reactor ??? Fixed Bed and Moving Bed are used TUDelft R

&CE

Reactors for Catalytic Reforming

Gas flow Gas flow

Catalyst bed

Axial-flow reactor

Radial-flow reactor

TUDelft

&CE

Semi-Regenerative Catalytic Reforming (SRR)

Hydrogen recycle Net hydrogen

C4770 K 780 K 790 K

Furnace

Reactor
720 K 760 K 780 K

Reformate Pretreated naphtha feed Catalytic reforming section Hydrogen separator Stabilizer

TUDelft

&CE

Continuously-Regenerative Catalytic Reforming (CRR)

Catalyst recycle Hydrogen (fresh & recycle) buffer drum

Naphtha (desulfurized)
Air Cl2

Reformate
Collectors

Lift pots Lift gas Reactor 1 Reactor 2 Reactor 3 Reactor 4

Regenerator

Reactors

TUDelft

&CE

Operating conditions in catalytic reforming

semi H2/HC (mol/mol) Pressure (bar) Temperature (K) Catalyst life 10 15-35 740-780 0.5-1.5 y fully 4-8 7-15 740-780 days-weeks continuous 4-8 3-4 770-800 days-weeks

H Cl O Pt -Al-O-Al-O-Al-O-Al-O-Al-Al2O3

TUDelft

&CE

Catalytic Reforming Typical Feedstock and Product Composition (vol%)

Component Alkanes Alkenes Naphthenes Aromatics

Feed 45 55 02 30 40 5 10

Product 30 50 0 5 10 45 60

TUDelft

&CE

Alkylation

TUDelft

&CE

Modern oil refinery

LPG and Gas LPG Straight run gasoline Atmospheric Distillation LPG Naphtha Middle distillates Heavy atm. gas oil Vacuum gas oil Solvent extraction Lube base stocks Hydrotreating Catalytic reforming Reformate Gasoline Hydrotreating Hydrotreating Cycle oil Hydrocracking Gasoline, Naphtha, Middle distillates Solvent dewaxing LPG and Gas Gasoline, Naphtha, Middle distillates Visbreaker Delayed coker / Flexicoker Fuel oil Asphalt Gasoline, Naphtha, Middle distillates Industrial fuels Coke Lube oils Waxes Catalytic cracking Gasoline Slurry oil Treating and Blending Solvents Kerosene Diesel Heating oil Lube oil Greases Asphalt Alkylation Alkylate Refinery fuel gas

Crude oil

Vacuum Distillation

Propane deasphalter

TUDelft

&CE

Alkylation
Aim Conversion of alkenes & alkanes to higher branched alkanes

alkylate: high octane number gasoline

Past
Thermal process ( 770 K, 200-300 bar)

Nowadays
Catalytic process ( 298 K, 8 bar) H2SO4 / HF / AlCl3-HCl

TUDelft

&CE

Example of Alkylation

C C C C

C C C

C C C C C C C C C C C C C C C C C C C C C C C C C

38 % 16 %

4% 25 %

+ small amounts of other products

TUDelft

&CE

Alkylation Mechanism
Reaction via Carbenium Ions
Initiation C C C C C C C Propagation C C C C C C C C C C + C Etc.
+ +

+ +

C C C
+

C C C

C C C C
+

C C C

C C C

C C C C C C C C C C C C C + C

C C C C

C C C C

TUDelft

&CE

Alkylation
Feedstocks?
i-butane C-C=C C-C-C=C

FCC, Hydrocracking, Distillation, .... FCC, coking

Practical (dis)advantages two common catalyst systems H2SO4 10 oC 100 HF 30 oC 0.5

kg acid consumption/t alkylate

TUDelft

Heterogeneous catalyst would be a breakthrough

&CE

Alkylation, summary
i-C4/alkene should be large (5 - 15) Inorganic acid phase: accumulation C-C=C mixing essential Acid catalysts H2SO4 (95%, 1% H2O) HF (90%, 1% H2O) Highly exothermic reactions What catalyst do you prefer?? H2SO4 most active, but by-products HF less active, but hazardous

TUDelft

&CE

Alkylation with H2SO4 in Cascade of CSTRs

Recycle isobutane Receiver Propane

Depropanizer
n-Butane

Economizer

Vapor (i-C4 / C3) caustic water

Alkene
Recycle acid Fresh acid spent caustic Reject acid waste water

Alkylate

Isobutane

Reactor & Acid settler

Caustic scrubber

De-isobutanizer Debutanizer

TUDelft

&CE

Alkylation with H2SO4 in Stratco contactor with autorefrigeration

PC

Settler Alkylate & C3 + C4 Emulsion (HCs/acid)

Recycle acid

To condenser and separator Reactor

TUDelft

Alkene & isobutane feed

Recycle C3 + C4

&CE

Comparison of H2SO4 and HF Alkylation

Temperature (K) Pressure (bar) Residence time (min) Isobutane/butene feed ratio Acid strength (wt%) Acid in emulsion (vol%) Acid consumption per mass of alkylate (kg/t)

H2SO4 process 277 283 26 20 30 8 12 88 95 40 60 70 100

HF process 298 313 8 20 5 20 10 20 80 95 25 80 0.4 1

TUDelft

&CE

Conversion of heavy residues

TUDelft

&CE

Modern oil refinery

LPG and Gas LPG Straight run gasoline Atmospheric Distillation LPG Naphtha Middle distillates Heavy atm. gas oil Vacuum gas oil Solvent extraction Lube base stocks Hydrotreating Catalytic reforming Reformate Gasoline Hydrotreating Hydrotreating Cycle oil Hydrocracking Gasoline, Naphtha, Middle distillates Solvent dewaxing LPG and Gas Gasoline, Naphtha, Middle distillates Visbreaker Delayed coker / Flexicoker Fuel oil Asphalt Gasoline, Naphtha, Middle distillates Industrial fuels Coke Lube oils Waxes Catalytic cracking Gasoline Slurry oil Treating and Blending Solvents Kerosene Diesel Heating oil Lube oil Greases Asphalt Alkylation Alkylate Refinery fuel gas

Crude oil

Vacuum Distillation

Propane deasphalter

TUDelft

&CE

Conversion of Heavy Residues

Why? Product distribution not right
Demand for lighter products Demand for cleaner products low/zero sulfur gasoline and diesel

How? Carbon out

Coking processes

Hydrogen in
Hydrotreating

Heavier, more sulfur containing, crudes are processed Stricter regulations on refinery emissions

TUDelft

&CE

Light Crude Oil Product Distribution

Hydroskimming refinery LPG Gasoline Kerosene / Gas oil 2% 15% Complex refinery LPG Gasoline 4% 28%

35.5% Kerosene / Gas oil 39%

Fuel oil
(3.5% sulfur)

44% Fuel oil

(3.5% sulfur)

22% 7%

TUDelft

Own use

3.5%

Own use

&CE

Impact on refinery
Deep conversion: whitening of the barrel
More hydrotreating facilities Production capacity for H2 production Production of refinery fuel gas for heating (instead of using heavy oil fraction) Production capacity for conversion H2S End-of-pipe solutions

TUDelft

&CE

Flexicoking
Carbon Out Thermal cracking
Residual oil gas, liquid, coke

Coke gasification / combustion

C + O2 C + H2O C + CO2 CO CO + H2 2 CO exo endo endo

Process scheme? TUDelft R

&CE

Flexicoking
Liquid products to fractionator
Cyclone Water Venturi scrubber Separator Sulfur Coke slurry Sulfur removal

Low calorific gas

Composition?

Scrubber

Steam

Coke fines

1000 1100 K

Feed
750 - 800 K

1200 - 1300 K

Product yields
Steam Purge coke Air

Gas and LPG Naphtha,Gasoil Coke

10 - 15 % 55 - 65 % 25 - 30 %

Reactor

Heater

Gasifier

Thermal cracking Heat exchange

Combustion/Gasification

TUDelft

&CE

Catalytic Hydrogenation of Residues

What are the differences with thermal processes??
Catalytic Processes
Catalyst deactivation Metal deposition Coke deposition Molecular size large Diffusion limitations to be expected High hydrogen pressure

Process design? Technology based on (semi)continuous catalyst replacement

Fluidized-bed reactors, small catalyst particles Moving-bed reactors, catalyst particles with wide pores Slurry reactors, very small catalyst particles

TUDelft

&CE

Catalyst Deactivation
Deposition of poisons
Asphaltenes, coke Metals as metal sulfides Ni-porphyrin + H2 V-porphyrin + H2 NiS + hydrocarbons V2S3 + hydrocarbons

TUDelft

&CE

Catalyst Deactivation during hydrotreating

fresh catalyst active site poisoning pore plugging

catalyst pellet

. . . . .... .. . . . .. . . . . .... . .. . . pore .... . . ... . . . .... . . .. .. .

metal sulfide deposit ..

.......... .. . . . . . .. . .... . ..... . . .. .. .. .. . . ... . ... . . . .. .... ...... .. .... . .. . . .... . . ... . . . .... . . .. .. .

micro scale

active site

.. . .. . . . . .. . . ... . . . .... . . .. .. .

time on stream

TUDelft

&CE

Reactors for Hydroconversion of Residues

Gas + liquid Product Distributor Inert beads Catalyst bed Support grid Product Gas Level of fluidized bed Gas bubble Catalyst in suspension Gas Liquid +cat. Product (+ cat.)

Gas bubble Catalyst in suspension

Liquid

Fixed-bed reactor (trickle flow)

TUDelft

Fluidized-bed reactor (three phase)

Slurry reactor

&CE

Process with Fluidized-bed Reactors (Lummus)

Hydrogen

Catalyst addition

700 - 740 K 150 - 200 bar

Off gas Purification

High pressure separators

Hydrogen rich gas Catalyst removal Low pressure separator Fractionation

Feed

Products

Heaters

Reactors

Separation

TUDelft

&CE

HYCON Process
Hydrogen

Feed
620 - 710 K 100 - 200 bar Moving catalyst bed

Stationary catalyst bed Hydrogen Stationary catalyst bed

Spent catalyst Fresh catalyst Catalyst rejuvenation

Products to separation

HDM bunker reactor

HCON fixed-bed reactor

TUDelft

&CE

HDM Catalyst Rejuvenation

Used catalyst

Sulfur removal

Extraction

Drying

Classification Rejuvenated catalyst

TUDelft

&CE

Processes with Fixed-bed Reactors

Residual feed

HDM catalyst Metal content (ppmw) < 25 25 - 50 50 - 100 > 100 >> 100 Moving bed Bunker HDM Bunker HDM Cat. rejuvenation

HDS catalyst wide pores

HDS catalyst narrow pores

Fixed bed Fixed bed, dual catalyst system Fixed bed, threefold catalyst system Fixed bed, HDS catalysts Fixed bed, HDS catalysts

TUDelft

&CE

Veba Combi-Cracking Process (Slurry Reactor)

Hydrogen

700 - 740 K 150 - 300 bar

Off gas Purification

HP separator Catalyst LP separator

Cold LP separator

Products
Fractionation

Feed Heaters Slurry reactor

Residue

Fixed-bed reactor

TUDelft

&CE

Treatment refinery gas streams

TUDelft

&CE

Treatment of Refinery Gas Streams

Removal of H2S
Exhaust from hydrotreating Exhaust from FCC

Removal of NOx, SO2

Exhaust from burners Exhaust from FCC regenerator

Recovery of H2
Exhaust from hydrotreating Exhaust from FCC

TUDelft

&CE

H2S Removal and Conversion

Removal by absorption in regenerable liquid solvents Alkanolamines
HO CH2 CH2 NH2

MEA (mono-ethanol amine)

CH3 CH CH2 N CH2 CH CH3 DIPA (di-iso-propanol amine) OH H OH

Conversion of H2S to elemental S:

Claus process SCOT process (S-compounds H2S Claus plant) SuperClaus process

TUDelft

&CE

H2S removal by amine absorption

Purified gas Lean alkanolamine solution H2S to sulfur recovery

315 K

385 K

Feed gas Rich solution Absorber Regenerator

LP steam

TUDelft

&CE

Claus Process
H2S oxidized to elemental S: 2 H2 S + O2 S2 + 2 H2O H0298 = - 444 kJ/mol

Sulfur recovery limited by equilibrium Claus: About 95% H2S converted to S SCOT & SuperClaus: nearly 100% recovery

TUDelft

&CE

Claus Process
H2S + 3/2 O2 2 H2S + SO2
Reheater HP steam 520 K > 1300 K QC LP steam Air H2S :SO2 2 :1

SO2 + H2O 3/2 S2 + 2 H2O

Tail gas

Acid gas

Boiler feed water Boiler feed water Sulfur pit Sulfur pump

Liquid sulfur

Reaction furnace

Waste heat boiler

Claus reactor 1 Condenser 1 Condenser 2

Claus reactor 2 Condenser 3

Claus reactor 3 Condenser 4

TUDelft

&CE

SCOT Process
SO2, CS2, COS + H2 H2 S
Treated gas Acid gas recycle to incinerator to Claus plant Air Fuel gas Reducing gas Claus tail gas
570 K LP steam

LP steam Purge

Line burner SCOT reactor

Cooling tower

Absorber

Regenerator

TUDelft

&CE

SuperClaus Process
SuperClaus reaction: H2S + 1/2 O2
Reheater
HP steam > 1300 K LP steam Boiler feed water
Q C

1/2 S2 + H2O

Tail gas

H2S 0.8-3 vol%

Acid gas Air Reaction furnace

Boiler feed water

S Claus reactor 1

S Claus reactor 2

S Selective oxidation reactor Condenser 4

Waste heat boiler

Condenser 1

Condenser 2

Condenser 3

TUDelft

&CE

Recovery of Hydrogen from Refinery Gas Streams

Methods:
Cryogenic distillation Energy intensive Absorption High purity can not be obtained Adsorption TSA (Temperature Swing Adsorption) PSA (Pressure Swing Adsorption) Membrane separation

TUDelft

&CE

Adsorption
Applications:

Air drying N2 production H2 purification: H2 hardly adsorbs

Transient process: cyclic

Adsorption of impurities Regeneration of adsorbent bed

by raising T: TSA by reducing p: PSA

TUDelft

&CE

Hydrogen purification using PSA

Purified hydrogen

Depressurization / Pressurization Depressurization / Purge

Adsorber 1

Adsorber 2

Adsorber 3

Adsorber 4

Feed

10 - 40 bar Pressurization

1 - 10 bar Purge gas Regeneration / purge Depressurization

Adsorption

TUDelft

&CE

Cycle-sequence in PSA
Step 1
Adsorption

Step 2

Step 3

Step 4

Adsorber 1
Regeneration Adsorption

Adsorber 2
Pressure
Regeneration Adsorption

Adsorber 3

Regeneration Adsorption

Adsorber 4

Regeneration

Time

TUDelft

&CE

Membranes: important properties

High selectivity High permeability High mechanical stability Thermal stability Chemical resistance

TUDelft

&CE

Membranes: Applications
Dialysis Seawater desalination Membrane distillation Concentration of proteins in food industry Separation of gas mixtures

TUDelft

&CE

Membranes
Polymeric membranes
Advantage high selectivity Disadvantages limited thermal stability (180 oC) prone to degradation

Inorganic membranes Pd, porous layers

Advantages stable at high temperature large variety of materials Disadvantage generally low selectivity

TUDelft

&CE

Membrane Processes Advantages and Disadvantages

Advantages
Low energy consumption no phase transfer Mild conditions Low pressure drop No additional phase required Continuous separation Easy operation No moving parts

Disadvantages

Fouling Low lifetime Often low selectivity No economy of scale (scale-up factor ~ 1)

TUDelft

&CE

Monsanto hollow-fiber Module

Feed (pmax = 148 bar)

Fiber bundle end seal

Permeate

Retentate

D = 0.1 - 0.2 m

Potted open end

Fiber bundle

L=3m

TUDelft

&CE

Applications in Gas Separation

Feed gas H2-N2, CH4, Ar H2-CH4, N2 H2-CO H2-enriched gas CO2-CH4 N2-concentration Application Ammonia synthesis gas Methanol synthesis gas Synthesis gas in the Chemical industry refineries, chemical industry Natural gas Biogas Inertization Total capacity (m3 (STP) h-1) 390400 6100 12540 164300 34100 310 800

TUDelft

&CE

Hydrogen Recovery in Oil Refineries

Catalytic Reformer Naphtha Hydrodesulfurization
Permeate 6.4 Nm3 h-1 17 bar 92% H2

Refinery products Hydrodesulfurization

Cracking products Hydrodesulfurization

Feed 20 Nm3 h-1 48 bar 60% H2

Retentate 13.6 Nm3 h-1 48 bar 55% H2

Gas oil Hydrodesulfurization

Membrane units
Heating gas

TUDelft

&CE

Novel processes for high-quality gasoline and diesel

TUDelft

&CE

Reformulated Gasoline
Prior to 1973
reformate + tops + lead

From 1973 on
lead-free gasoline enhance ON by catalytic reforming, isomerization,

Maximum sulfur, alkene, benzene content Minimum oxygenate content

Best gasoline
alkylate but not attractive process

TUDelft

&CE

Diesel

Source* Straight-run gas oil Light cycle oil from FCC Gas oil from thermal processes Gas oil from hydrocracking Fischer-Tropsch gas oil * Before hydrodesulfurization

Sulfur (wt%) 1 1.5 2 2.8 23 < 0.01 0

Aromatics (wt%) 20 40 > 70 40 70 < 10 0

Cetane number 40 50 < 25 30 50 > 55 > 70

TUDelft

&CE

TUDelft
Diameter (nm)
0.0 n-butane iso-butane neopentane benzene p-xylene o-xylene ammonia (C4H9)3N (C4F9)3N water hydrogen carbon monoxide carbon dioxide oxygen nitrogen 0.2 0.4 0.6 0.8 1.0

Shape Selectivity

4A

X,Y

ZSM-5

&CE

Shape Selectivity
+

Reactant selectivity

Transition-state selectivity

Product selectivity

CH3OH

H2 O

TUDelft

&CE

Routes to MTBE and ETBE

CH3 H3C C CH2 + CH3OH

CH3 H3C C O CH3 CH3

MTBE

CH3 H3C C CH2 + CH3CH2OH

CH3 H3C C O CH2CH3 CH3

ETBE

TUDelft

&CE

Routes to Isobutene
n-butane C C C C n-butene C C C C

Isomerization

Isomerization

C C C C iso-butane

Dehydrogenation

C C C C iso-butene

TUDelft

&CE

Butene Isomerization in Ferrierite

C C C C

double bond isomerization

C C C C

C C C C + C C C C C C C C C C C C + C C C C C C C C C C C C +

H+ c C C C

skeletal isom. +
C C C C C C C C

skeletal isomerization
C C C C C C C C C + C C C C C C C +

Ferrierite

C C C C

C C C C

TUDelft

&CE

Butene Isomerization
C4 product 620 K 1 2 bar

C4 feed Heater Reactor Compressor Distillation

C5+

TUDelft

&CE

Isomerization of Hexanes - Equilibrium Composition

0.7

Mol fraction C6 isomers in total hexanes (-)

0.6 0.5 0.4 0.3 0.2 0.1 0 300

C C-C-C-C C C C-C-C-C-C C C-C-C-C-C C-C-C-C-C-C

CC C-C-C-C
350 400 450 500 550 600 650 700

Temperature (K)

TUDelft

&CE

Effect of n-Alkane Recycle on Octane Number

92 90 88

with recycle of normal alkanes

RON

86 84 82 80 300

Feed: Pentanes 60% Hexanes 30% Cyclics 10%

once through process

Pt/Cl/Al2O3
350 400 450

Pt/H-Mordenite
500 550 600

TUDelft

Temperature (K)

&CE

TIP (Total Isomerization Package) Process

HYSOMER lead C4

C5/C6 feed

HYSOMER

ISOSIV

normal alkanes recycle

iso-alkanes iso-alkanes C4

ISOSIV lead

C5/C6 feed

ISOSIV

HYSOMER

TUDelft

normal + iso alkanes recycle

&CE

From Synthesis Gas to Gasoline and Diesel

Process MTG MTO MOGD Fischer-Tropsch

via methanol methanol alkenes synthesis gas

Main product(s) gasoline alkenes for MOGD process distillates/gasoline distillates

TUDelft

&CE

MTG (Methanol to Gasoline) Process

2 CH3OH H3C-O-CH3 Light alkenes + H3C-O-CH3 Heavy alkenes Aromatics + H3C-O-CH3

H3C-O-CH3 + Light alkenes + Heavy alkenes + Aromatics + Higher aromatics +

H2O H2O H2O Alkanes H2O

TUDelft

&CE

MTG (Methanol to Gasoline) Process

70

Product distribution (wt%)

60 50 40 30 20 10 0 10-4

Methanol Water

DME

Alkanes (+ C6+ alkenes) Aromatics C2-C5 alkenes

10-3 10-2 10-1 1 10

Space time (hm3reac/m3liq)

TUDelft

&CE

Mobil MTG Process

22 bar 620 K

Purge gas to fractionation

580 K

690 K

690 K

Gasoline to fractionation
Water

Crude methanol DME Reactor Conversion reactors Swing reactor being (ZSM-5) regenerated

TUDelft

&CE

Mobil MOGD (Methanol to Gasoline and Distillates) Process

Gasoline recycle Alkene feed

LPG

470 - 530 K 30 - 100 bar Gasoline

Distillate to hydrotreating Furnace Adiabatic oligomerization reactors Separators

TUDelft

&CE

Gas-to-Liquid Syngas & Fischer Tropsch

TUDelft

&CE

Gas-to-Liquid Conversion
Syngas generation Fischer-Tropsch synthesis Fuel upgrading

Feed

Coal, oil, natural gas, biomass Remote natural gas resources Associated gas crude oil rigs Monetising alternative to flaring, re-injection Political drive New products Chemicals source in future? High-quality clean fuels More efficient utilization fossil resources Renewable, contributes to sustainable society

Flexible technology

Lower environmental impact

TUDelft

&CE

Production Synthesis Gas

5.1, 5.2, 5.4 Important base chemical for variety of applications
Mixtures H2 3 H2 : 1 N2 2 H2 : 1 CO 2 H2 : 1 CO 1 H2 : 1 CO CO
Feedstock??

Main uses Refinery hydrotreating and hydrocracking Ammonia plant feed Alkenes (Fischer-Tropsch reaction) Methanol plant feed Aldehydes and alcohols (Oxo reactions) Acids (formic and acetic)

Hydrocarbons natural gas, oil,coal biomass Steam reforming Partial oxidation

Future for H2 Solar?? R

Process??

TUDelft

&CE

Reactions starting from CH4

Steam reforming Water gas shift CO2 reforming Thermal cracking Boudouard reaction Partial oxidation Complete combustion CH4 + H2O CO + H2O CH4 + CO2 CH4 2 CO CH4 + O2 CH4 + 2 O2 CO + 3 H2 CO2 + H2 2 CO + 2 H2 C + 2 H2 C + CO2 C + 2 2

Hr = 206 kJ/mol Hr = - 41 kJ/mol Hr = 247 kJ/mol Hr = 75 kJ/mol Hr = -173 kJ/mol Hr = -36 kJ/mol Hr = -803 kJ/mol

C2 + 2 2

TUDelft

What reaction(s) are most attractive??

&CE

Conversion Routes to Synthesis Gas

Natural gas Heavy oil fraction H2 O O2/air Air/O2/(H2O) Autothermic reforming Carbon removal Sulfur removal Purification Adjustment Purification Adjustment Partial oxidation Coal

Desulfurization H2 O Steam reforming

Pulverization H2 O O2/air Gasification

Sulfur removal Purification Adjustment

Carbon monoxide, methanol, ammonia, hydrogen, etc.

TUDelft

&CE

Steam Reforming Thermodynamics H2O/CH4 = 1

Heat required ???

H2/CO = 3

?
Temperature
R

TUDelft

&CE

steam reforming versus partial oxidation

Equilibrium Compositions

Steam reforming H2O/CH4 = 1

Partial oxidation O2/CH4 = 0.5

H2/CO = 3

H2/CO = 2

TUDelft

&CE

Thermodynamics steam reforming

Effect of Temperature and Pressure
H2O/CH4 = 1

With increasing pressure TUDelft lower conversion more CH4 R

&CE

Process Design
T, p ???? Heat management? Full conversion?

TUDelft

&CE

Typical Allothermal Steam Reforming Process

Steam BFW Cooling water

Raw syngas

Tubes filled with catalyst

L = 7 - 12 m dt = 70 - 130 mm 500 - 600 tubes

Fuel Air Superheated HP Steam BFW

Convection section Radiation section

Condensate Flue gas to stack

Material tubes
Ni-Cr alloy up to 1150 oC (Tm = 1370 oC) More expensive materials at higher T
Process steam CO2

Natural gas Reformer Desulfurizer Knock-out drum

TUDelft

Optimal tube diameter??

Heat transfer with dt Pressure drop with dt

&CE

Steam Reformer

Radiant section

Convection section Air preheater

ISO VIEW

FRONT ELEVATION

TUDelft

&CE

Typical Reformer Conditions Industrial Processes

Process Hydrogen Hydrogen1) Ammonia Methanol Aldehydes/ alcohols Reducing gas
1) 2)

H2O/C (mol/mol) 2.5 4.5 3.7 3.0 1.8 1.15

Texit (K) 1123 1073 1073 1123 1138 1223

pexit (bar) Composition (vol%)2) H2 CO CO2 CH4 48.6 9.2 5.2 5.9 27 34.6 5.3 8.0 2.4 27 39.1 5.0 6.0 5.5 33 50.3 9.5 5.4 2.6 17 28.0 25.9 19.7 1.1 17 70.9 22.4 0.9 1.5 5

From naphtha Rest is H2O

Critical points??? TUDelft

Excess H2O CH4 slip

&CE

Methane slip
60 80

Methane slip (% unconverted)

Methane slip (% unconverted)

50 40 30 20 10

30 bar 20 bar

H2O/CH4 = 3

70 60 50 40 30 20 10 0 1000 1050 1100

p = 30 bar
H2O/CH4 = 1 H2O/CH4 = 2 H2O/CH4 = 3 H2O/CH4 = 5

10 bar

0 1000

1 bar 1050 1100 1150 1200

1150

1200

Temperature (K)

Temperature (K)

Practical conditions TUDelft

H2O/CH4 = 2.5 - 4.5 T: 1090 - 1150 K P: 7 - 30 bar R

&CE

New Processes
Coke problem, in particular for heavy feed stocks
pre-reformer at low temperature

Investment large
autothermic reforming

Exergy loss enormous

membrane reactor equilibrium is shifted (palladium for H2 permeation) O2 plant avoided (O2 permeation from air)

Other chemical routes

methane (catalytic partial oxidation, CPO) ethane (catalytic partial oxidation) methanol (catalytic decomposition)

TUDelft

&CE

Steam Reformer with Prereformer

Fuel Air Flue gas to stack Superheated HP Steam BFW

770 K
Hot raw syngas Desulfurizer

Process steam Feed Reformer Pre-reformer

TUDelft

CnHm + H2O CH4 + CO2/CO

&CE

Autothermal Reforming
Oxygen
Molar feed ratio H2O/CH4 = 1 - 2 O2/CH4 0.6 Burner

Natural gas Steam

CH4 + O2 CO + 2 H2

Combustion zone CH4 + 2 O2 CO2 + 2 H2O 2200 K

CH4 + H2O CO + 3 H2 CH4 + CO2 2 CO + 2 H2

Reforming zone 1200 - 1400 K

Catalyst bed

20 - 100 bar

TUDelft

Syngas

Composition syngas? Why O2, not air? Investment high or low? T-profile in reactor? R CE

&

Heat-integrated Reformers
Hot gas from the autothermal reformer used for steam reforming
Natural gas Steam Oxygen Syngas

Syngas
Dense phase with catalyst Catalyst Catalyst

Oxygen Natural gas Steam Gas-heated reformer Autothermic reformer Combined autothermic reformer

ICI Combined Reforming

Exxon CAR

TUDelft

&CE

Exergy
Quality of energy in > quality of energy out
(quantity remains the same: first law)

Exergy losses in process

External losses emissions to environment (e.g. in off-gas), similar to energy losses (spills) Internal losses physical (heat exchange, compression) & chemical (depend on process and reaction conditions)
rest 9% reformer 29%

distillation 8% methanol synthesis 7%

rest 7%

Exergy analysis methanol production (ICI)

TUDelft

distillation 38%

methanol synthesis 24%

reformer 78%

Energy spill

Exergy loss

&CE

Methane (Hydrocarbon) Partial Oxidation

Non-catalytic partial oxidation (SGP process)
Very high temperature (1650 K) Small amounts of soot are produced extensive gas-clean-up

Catalytic partial oxidation (CPO)

Relatively low temperature (900 1300 K) Less loss of exergy Less severity for materials No soot formation Very fast reaction (residence time, 0.5 4 ms) small equipment No commercial process yet exists

Both processes require pure oxygen (capital intensive cryogenic distillation)

TUDelft

&CE

Mechanism and Thermodynamics (CPO)

O2
Mildly exothermal
En do the rm

Dominant pathway depends on:

Catalyst (and support)
Rhodium direct CO + H2 formation Ruthenium combustion-reforming
al

CH4
O2
Hi O2 ghly ex o

CO + H2
CH4
th er

CO2 + H2O
m al

Oxygen partial pressure

Coke formation occurs at low O2 partial pressure

Synthesis gas formation is favored by:

Low pressure High temperature CH4:O2 2

TUDelft

&CE

Considered Reactor Types

Synthesis gas Synthesis gas Synthesis gas

Immobile catalyst
Fixed bed (Foam) Monolith Gauze Coated wall
Reduced cat.

Reactant feeding
Continuous flow Reverse flow Alternating flow O2CH4O2 O2 membrane
Methane Oxygen Methane Oxygen

Oxidised cat.

riser

TUDelft

Fluidized bed reactor

Air

Methane

Riser reactor

&CE

Reactor Temperature Profile

Hot spot formation
1400 T up to 600 K promotes Catalyst sintering Active metal evaporation Migration of active metal into support Coke formation Detrimental to catalyst stability

Temperature (oC)

> pO2

< pO2 Adiabatic Temperature

1000 600
mainly total oxidation

mainly reforming

Solution?
increase heat-transfer

Catalytic bed length (-)

TUDelft

&CE

Commercial CPO Process

Requirements:
Good catalyst stability
Mechanical (fluid bed and riser reactor) Activity and selectivity

Cheap oxygen supply (oxygen separation membrane)

Inside or outside reactor

High flow rate (small equipment) High catalyst activity Limited mass transfer limitation (catalyst utilization, expensive noble metals) Suppression of total oxidation reactions (hot-spots) Good conductive heat-transfer Internal heat-exchange

TUDelft

&CE

CPO (Fuel Cell Application)

Exothermal processes
Oxygen

Hydrocarbons (Petrol, Diesel) or Natural Gas

Vaporizer CPO WGS CO ox

H2 + CO2 Water Fuel Cell Air

H2O + CO2

TUDelft

&CE

Production Raw Syngas for NH3 synthesis

N2 + 3 H2 2 NH3 Background
O-containing molecules poison ammonia synthesis catalyst (Fe) purification steps; CO removal, CO2 removal
H2 CH4
670 K 660 K 770 K 1020 K 1020 K 1270 K

Desulfurization 24 + 27 m3 Steam

Steam reforming 17 m3 Air

Autothermic reforming 33 m3

640 K Component (mol%) H2 N2 CO CO2 CH4 Ar

710 K

490 K

510 K

590 K

640 K

56.34 22.20 12.76 8.18 0.22 0.30

HT CO Shift 57 m3

60.02 20.16 3.33 15.85 0.21 0.25

LT CO Shift 61 m3

61.15 19.77 0.40 18.24 0.20 0.24

CO2 removal

74.68 24.10 0.49 0.20 0.24 0.29

Methanation 25 m3

74.06 24.69 < 5 ppm < 5 ppm 0.95 0.30

To compression & ammonia synthesis (61 m3)

TUDelft

&CE

CO conversion: Water-gas shift CO + H2O CO2 + H2

13 mol% CO

Kp

Kp =

p H 2 pCO2 pCO p H 2O

640 K

490 K

HT shift
710 K

LT shift
510 K

Temperature (K)

Moderately exothermal Favourable: low T

0.4 mol% CO too high for Fe catalyst R

TUDelft

&CE

CO conversion
Remaining CO removed by methanation CO + 3 H2 CH4 + H2O
But first CO2 removed by absorption

Removal system MEA MEA with inhibitors K2CO3 with additives MDEA with additives TUDelft

GJ/mol CO2 210 93-140 62-107 40-60 R

&CE

Fischer-Tropsch

TUDelft

&CE

Fischer-Tropsch Process Product distribution

par 6.3

Large variety: CH4. CO, CO2, H2O, alkanes, alkenes

Main reactions Alkanes Alkenes Water-gas shift Side reactions Alcohols Boudouard reaction n CO + (2n + 1) H2 Cn H2n + 2 + n H2O n CO + 2n H2 CnH2n + n H2O CO2 + H2 CO + H2O n CO + 2n H2 H(-CH2-)nOH + (n-1) H2O 2 CO C + CO2

Product distribution depends on

Catalyst Conditions

T, pCO, pH2, ptot

TUDelft

Reactor Process design

&CE

Fischer-Tropsch Process - Mechanism

CO + H2
initiation termination

Product probability

CH2
propagation

1-

CH4

1-

C2H4
propagation

1-

C2H6

(1-)

propagation

CnH2n

1-

CnH2n+2

n -1 (1-)

TUDelft

&CE

Fischer-Tropsch synthesis
1 0,9 0,8
mass fraction

CO + 2H2
methane

CnH2n+2 + H2O
wax

Kinetic scheme
C*

C2 *

1-

CH4 C2H4 C2H6 C3H6 C3H8 C4H6 C4H10

0,7 0,6 0,5 0,4 0,3 0,2 0,1 0 0 0,2 0,4 0,6 chain growth probability

gasoline ethane propane butane

diesel

C3 *

C4 *

0,8

C5 *

...

...

TUDelft

, Process?

What products would you try to synthesize?

&CE

Anderson-Schulz-Flory Distribution
1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0 0.2 0.4

methane

wax

mass fraction

gasoline ethane propane butane

0.6

diesel

0.8

chain growth probability

Maximum diesel selectivity 39.4% with = 0.87 How to maximise diesel???

TUDelft

high catalyst and subsequent cracking of wax

&CE

Reactor design??
Reaction highly exothermal Temperature influences product distribution
Highly dependent on catalyst, roughly > 530 K carbon deposition < 570 K wax deposition Viscosity product mixture increases at lower T

H2/CO ratio influences product distribution Paraffins do not react further Olefins do react
To paraffins Insertion

TUDelft

&CE

Fischer-Tropsch Process - Reactors

Multi-tubular fixed-bed reactor
Syngas Gaseous products Products
Steam Cooling oil in

Riser reactor

Slurry reactor

Cooling oil out

Steam

Liquid products

Cooling water

Gaseous products

Standpipe Slide valves Riser

Cooling water

Liquid products

Syngas

Syngas

TUDelft

&CE

Fischer-Tropsch Process - Comparison of Reactors

Multi-tubular fixedbed reactor Conditions Inlet T (K) Outlet T (K) Pressure (bar) H2/CO feed ratio Conversion (%) Products (wt%) CH4 C2H4 C2H6 C3H6 C3H8 C4H8 C4H10 C5 C11 (gasoline) C12 C18 (diesel) C19+ (waxes) Oxygenates 496 509 25 1.7 60 66 2.0 0.1 1.8 2.7 1.7 2.8 1.7 18.0 14.0 52.0 3.2 Riser reactor 593 598 23 2.54 85 10.0 4.0 4.0 12.0 1.7 9.4 1.9 40.0 7.0 4.0 6.0 Slurry reactor 533 538 15 0.68* 87 6.8 1.6 2.8 7.5 1.8 6.2 1.8 18.6 14.3 37.6 1.0

TUDelft

&CE

Fischer-Tropsch Process - Sasol I

Air Oxygen plant N2 Phenols CO2, H2S O2 Coal Lurgi gasifiers H2O Coal Water Power plant Tar & oil work-up Naphtha Hydrogenation Electricity Road prime Creosote Pitch BTX Light Naphtha Heavy Naphtha

Separation Raw syngas Purification Naphtha

Fixed-bed FT

O2 H2O

Autothermal reformer Off-gas

Riser FT

Off-gas Separation To towngas, ammonia

To towngas, ammonia Aqueous phase

Separation C3, C4 Oxygenates work-up Alcohols Ketones Oligomerization LPG Gasoline Oil Oil work-up Gasoline Diesel Fuel oil

Wax Hydrogenation

Oil Oil work-up Gasoline Diesel

TUDelft

Waxes

&CE

F-T Process - Sasol II and III Product Work-up

Purified syngas Slurry FT

Separation Syngas

H2O

Oxygenates work-up

Alcohols Ketones

C12+

Hydrodewaxing Catalytic reforming

Diesel

Autothermal reformer

C7 - C11

Gasoline

C5 - C6

Isomerization

Gasoline

C1 - C4 CH4

CO2 removal

Cryogenic separation

C3 - C4

Oligomerization Ethene

LPG Gasoline

TUDelft

&CE

F-T Process - Shell Middle Distillate Synthesis (SMDS)

Fuel gas (including LPG) Syngas Wax synthesis Flash Wax conversion Naphtha Kerosene Gas oil

Distillation

H2

TUDelft

&CE

Most favourite FTS reactors

Slurry bubble column reactor
Liquid
Coolant out

Multi tubular fixed bed reactor

Liquid Gas

Gas

Coolant out

Coolant in

Coolant in

Gas

Liquid

Gas

Liquid

TUDelft

Nearly isothermal conditions Low pressure drop High catalyst efficiency Catalyst renewal Backmixing Catalyst attrition Moderate G/L mass transfer Liquid solid separation

Convenient Simple to scale-up

Low catalyst efficiency Heat exchange - T-profiles Pressure drop Even distribution

&CE

Fischer Tropsch Technology

Still room for improvements Systematic approach Structure in catalyst and reactor
Monoliths Staging Decoupling cooling - reaction

Staged slurry bubble column reactor Air-lift recycle reactor Monolith loop reactor Structured internals Subcooling

TUDelft

R Kinetics very important

&CE

Proton-Exchange-Membrane (PEM) Fuel Cell

Negative bus plate eHydrogen frame Anode Platinum catalyst Cathode Air frame Positive bus plate e-

e-

e-

e-

e-

e-

e-

e-

e- H2 eH+ eeH+

e- H2 eH+ H+ e-

H2
PEM Electricity

e- O2 eeee-

O2
ee-

e-

H2O

TUDelft

&CE