Naphtha Hydrotreating

Reliance Hydroprocessing Course 2009

Contents

Introduction
Feedstocks properties
Naphtha hydrotreating kinetics
Naphtha hydrotreating hardware
Pitfalls in naphtha hydrotreating
FCC naphtha processing
Coker naphtha processing

Introduction
Naphtha hydrotreating is found in every refinery
Naphtha feed to reformer must be very low in sulfur
Naphtha can be treated to upgrade properties for
gasoline blending:
Light coker naphtha
FCC naphtha
Steam cracked naphtha

Some difficult naphtha feeds can be converted into

reformate:
Heavy coker naphtha
Intermediate FCCU naphtha
3

Naphtha processing in the refinery

NHT

Isom
GASOLINE

NHT

CRUDE

Reformer

CDU
Jet/Diesel HT

HCPT

DIESEL

HC

LCOHT

VDU
FCC

FCCPT

Coker

Coker
NHT

FCC
NHT

Naphtha processing in the refinery

Naphtha
C4 - C11

C4 - C6

Isom

I-C4 N-C4=

Alky

C7 C11

Reformer

Isomerization
Converts straight chain parraffins to branched
isomers
Increases Octane

Catalyst is based on Platinum Chloride

Sulfur and Nitrogen are catalyst poisons
Water will leach Clorine from the catalyst
Catalyst will deactivate if water is present in the feed
Extensive feed drying
Constant Clorine addition

Sensitive to NH4Cl corrosion

6

Alkylation
Reacts Isobutene with N-Butane to form Isooctane
Very high octane
No contaminants

Either HF or H2SO4 based

extremely toxic and corrosive

Solid acid (zeolite) based alternatives are available

Alkyclean
Not applied yet on a commercial scale
Everybody wants to be the second

Reforming
Reforming converts paraffins and naphthenes into
aromatics
Increasing octane
Hydrogen as a byproduct

Reforming reactor cycle and catalyst type

determines value of feed sulfur removal
Cyclic units regenerate individual reactors often
Semi-regen units regenerate at end of cycle
CCR units regenerate continuously

Nitrogen in feed reacts with Cl in reforming catalyst,

creating NH4Cl salt in product recovery
8

Reforming Feed Specifications

Sulfur
Nitrogen
Arsenic
Lead
Water
Silicon

.
.
.
.
.
.

.
.
.
.
.
.

.
.
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.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

< 0.5 ppm

< 0.5 ppm
< 1.0 ppb
< 1.0 ppb
< 10 ppm
< 20 ppb

Virgin Naphtha Properties

C ru d e
B re n t

D e n s it y
0 .7 6 9

P + O /N /A
4 2 /3 4 /2 4

A r a b L ig h t

350

0 .7 4 2

6 5 /2 0 /1 5

A bu Dhabi

600

0 .7 4 7

6 5 /2 0 /1 5

B e rri

500

0 .7 4 6

6 5 /2 0 /1 5

B o n n y L ig h t

500

0 .7 4 6

6 5 /2 0 /1 5

M aya

400

W TI

200

N o r th S lo p e

130

4 0 /4 5 /1 5

8000

5 5 /3 2 /1 3

L lo y d M in is t e r

10

S u lf u r
30

6 0 /2 7 /1 3
0 .7 5 7

4 8 /4 5 /1 2

Cracked Naphtha Properties

Br. No.
(g/100ml)

Diene
(g/100ml)

Sulfur
(ppmw)

Nitrogen
(ppmw)

High Sulfur

90

15,000

500

Low Sulfur

80

1,000

200

High Sulfur

90

>5

10,000

1,000

Low Sulfur

80

2,000

450

FCCU

50

<0.5

1,200

100

Resid Hydrocracked

20-100

50-200

Origin
Visbreaker

Delayed Coker

11

Feedstock Summary
Often applied before processes that increase the
octane of the gasoline
Downstream processes based on Noble metals
These require very low S and N levels
Often < 0.2 ppmwt S and N

Virgin naphtha quality is very crude dependent

Cracked naphthas have significantly lower quality
High sulfur and often high nitrogen
(Very) hydrogen deficient
High Bromine and Diene numbers
12

First Order Kinetics Apply

Assuming Constant Pressure, Temperature:
Rate of Reaction (Concentration of Reactants)n
For naphtha applications first-order kinetics apply:

CF
k = LHSV ln
CP
Where k = rate constant, LHSV = space velocity, C =
Concentration of reactant of interest (e.g., S, N)

13

First Order Kinetics

7
HDS

HDO

ln(Co/Cp)

5
4
3

HDN

50% FCCU Naphtha

1,950 ppm Sulfur
40.5 ppm Nitrogen
45 Bromine No.

1
0
0.0

0.1

0.2
1/LHSV

14

0.3

0.4

Hydrogen Consumption in a NHT

For each 1 wt% sulfur removed from a feed:

mercaptan
sulfide
disulfide
thiophene

5 Nm3/m3
10 Nm3/m3
8 Nm3/m3
20 Nm3/m3

For each 1 wt% nitrogen removed from a feed:

pyridine
pyrrole

For each vol% olefin

For each vol% diolefin
For each vol% aromatic
15

60 Nm3/m3
45 Nm3/m3

1.3 Nm3/m3
2.5 Nm3/m3
4.2 Nm3/m3

Mercaptan Recombination
RSH
+H2
-H2

R=CH2

S
2
-H

S
2
H
-

+H

+H

S
2

R-CH3

Olefins and H2S can form mercaptans which increase the total
HDS activity requirement
Olefins can either be present in the feed or created by
cracking reactions near the reactor outlet
This becomes significant above 340 C
1 to 10 ppm additional S in product from this type of recombination

16

Kinetics Summary
Naphtha treating is a vapor phase reaction
HDS and HDN are first order reactions in naphtha,
but HDN is much slower than HDS
Hydrogen partial pressure is important
Function of recycle gas circulation rate.

Maximum temperature often set by onset of

recombinant sulfur reactions
Becomes significant at T > 340 C

17

Catalyst Selection
Relative level of sulfur and nitrogen determine the
preferred catalyst system
Olefins & diolefins determine need for catalyst size
and activity grading
Naphtha contaminants (i.e. Si and As) require
special metal trapping catalysts

18

Catalyst Selection

Feed Nitrogen (ppm)

1000

NiMo Catalyst is Optimal

100

10

do
e
B
Split

lys
a
t
a
fC

CoMo Catalyst is Optimal

1
1

10

100

1,000

Feed Sulfur (ppm)

19

t i ma
p
O
t is

10,000

Hardware Considerations
Reactor design
downflow
multi-reactor, series or parallel

Vaporization
vapor phase reaction
never in radiant section of furnace

Reactor effluent heat exchanger

even tiny leaks have profound influence on product sulfur

Pressure drop build-up

20

Typical Operating Conditions

Virgin Naphtha

Cracked Naphtha

Unit pressure, barg

20 - 30

45 - 65

LHSV, h-1

3 - 10

1-5

Temperature, C

250 - 340

240 - 340

H2:Oil, Nm3/m3

50 - 100

250 500

7 - 10

15 - 45

ppH2, barg

21

Pitfalls in Naphtha Hydroprocessing

Pressure drop buildup
Occurs most frequently with cracked feed stocks
Can be prevented and controlled by catalyst grading
technology and unit design

Metals removal
Si and As are the major problems
Requires special metal trapping catalysts to remain activity
maintenance and to increase holding capacity and

22

Pitfalls in Naphtha Hydroprocessing

Unit monitoring
Traditional normalization only done on difficult units
Requires extremely good analytical data

Heat exchanger leaks

Salts and corrosion
ammonium chloride
ammonium bisulfide

23

FCC Naphtha Hydroprocessing

Goal of FCC naphtha processing is reduced gasoline
sulfur
In specific cases olefin saturation may be desirable
Generally, the extra hydrogen consumption and obtained
octane loss due to olefin saturation is not desired.

Due to a potentially high exotherm in these units,

conventional HDS units and catalysts are not
suitable for selective hydrogenation.

24

FCC Naphtha Cut Properties

Property

IBP-75

75-126

126-149

149+

Cut yield

22%

30%

16%

32%

100%

S, ppm

75

100

200

600

250

N, ppm

20

75

35

Br. No.

100

75

45

25

70

Saturates

33

38

30

20

30

Olefins

65

50

30

20

45

Aromatics

12

40

60

25

RON

95

87

93

93

92

MON

81

77

81

81.5

80

Sulfur is predominately in the heavy cuts

Olefins are predominately in the light cuts
25

Full Range

Pre-treatment vs. Post-treatment

Pre-treatment favored by:
Improved FCCU yields/conversion
Process more sour and heavier crudes
Process high N feeds (cokers, West coast)

Post-treatment favored by:

Lower investment cost
Very low S products
Pre-treatment alone will not always be
sufficient to reach the specification
26

Pre-treatment vs. Post-treatment

Very deep VGO Pretreatment is required to make ULSG

27

Reactor System for

Processing Cracked Naphtha
Make-up

Purge

Compressor

Fuel Gas

Furnace

Olefin saturation
Guard
Reactor

HDS
Main
Reactor

Polishing
Trim
Reactor

HP Separator

LP Separator
Feed
Pump
28

Gasoline HDS

Split FCC naphtha into light and heavy fractions

Fully hydrotreat heavy fraction
Adjust split to meet sulfur target and minimize octane loss
Caustic treatment of light fraction
Additional mid range cut with hydrotreating and reforming can
reduce octane loss

3+ RON loss expected

Refinery needs to be octane long and relatively sweet
FCC naphtha needed (i.e. pretreated FCC feed)
29

Post-treatment Octane Loss

Hydrotreating full range naphtha is impractical in terms of
octane loss and H2 consumption
Hydrotreating heavy fraction may be feasible in octane long
refineries

30

FCC Gasoline Pool Octane Loss

RON

MON

Hydrotreat Full Range FCC Naphtha

7-10

3-4

Hydrotreat Heavy Fraction

3-4

1-2

FCC Naphtha HDS Technologies

Selective hydrotreating
SCANfining (ExxonMobil)
Prime G+ (Axens)

Hydrotreating + Isomerization
OCTGAIN (ExxonMobil)
ISAL (UOP/PDVSA)

Catalytic distillation
CDHDS+ (CDTech)

Selective adsorption
S-Zorb (Phillips)
31

SCANfining
Selective Naphtha HDS Technology
Low S feed

6
High S Feed
SCANfining I

Octane Loss (R+M/2)

SCANfining I, little or no new

investment
Small decrease in octane

High S feed

High S Feed
SCANfining II

Upgrading to SCANfining II
can control octane loss
30 - 40% incremental
investment
Full use of existing equipment

1
Low S Feed
SCANfining I

0
0

30

60

Product Sulfur (wppm)

32

90

Coker Naphtha Hydroprocessing

High Diene Number
High likelyhood of reactor pressure drop issues

High Bromine Number

Excessive reactor temperature rise

High Contaminant Levels

33

High HDS, HDBr and very high HDN requirements

High silicon removal activity needed
High silica capacity needed
High Arsenic tolerance required

Reactor System Design

for Coker Naphtha Treating
A three reactor system solves many difficulties in
coker naphtha treatment
Guard reactor: saturates diolefins and helps prevent
increasing pressure drop
Main reactor: removes silicon, sulfur, nitrogen and olefins
Trim reactor: combats recombinant sulfur

Two reactor versions of this system have been

developed to provide similar results
Careful catalyst selection and system design
required to maximize catalyst life in any system
34

Catalyst Selection
A graded bed of active support material to saturate
the diolefins and prevent reactor pressure drop
problems
An active catalyst with high capacity for silica to
remove the silicon, sulfur, nitrogen, and olefins
Dilution of the coker naphtha with virgin and other
naphtha to reduce the reactor temperature rise to a
manageable level
35

Bed Grading
Recommended bed grading for coker naphtha units

300 to 1200 mm of large rings (i.e. KG 55, KF 542-9R)

450 to 1200 mm of medium ring support (i.e. KF 542-5R)
150 mm. or more of 3 mm catalyst (i.e. KF 647-3Q)
the remaining bed of 1.3 mm catalyst

A large active support layer can be substituted for a

guard reactor
Experience is used to size the bed grading layers
36

HDN is Important
Nitrogen affects catalytic reformers
Affects the acidity of the noble metal CCR catalyst
Forms salts that deposit on compressors and exchangers

Virgin naphtha has very little nitrogen

CoMo catalysts are used for maximum HDS when naphtha
nitrogen is < 3 ppm

Coker naphtha contains high levels of nitrogen

Normally HDN controls catalyst life
In high sulfur naphtha a split bed of NiMo and CoMo can
be optimal
37

Silicon Can Control Cycle Length

Primary source of silicon in naphtha is anti-foam additives
used in the delayed coker
Silicon content is not constant
Increases at end of coking cycle
Increases as throughput is increased

Chemicals used during crude oil production or transportation

may contain Silicon based drag reducers
Silicon deactivates the catalyst as it deposits, and
breakthrough occurs before all catalyst is saturated with
silicon
Silica is a more potent catalyst poison after catalyst
regeneration
coker naphtha spent catalyst is seldom reused
38

Silica Content at Breakthrough (%)

Silica Capacity Depends on

Catalyst Size, Grade & LHSV
25
20
KF-844-1.3Q
15
KF-844-3Q

10

KF-841-1.3Q

KF-841-3Q

5
0
0

5
LHSV

39

10

Silicon Uptake (wt% on fresh catalyst)

Silicon Uptake Exhibits Adsorption Isotherm

Like Behavior
8
7
6
5
4
3
2
1
0

Section of Reactor
40

10

Summary
Reformer performance dictates naphtha treating requirements
Virgin naphtha treating is usually a relatively simple process
Cracked naphtha treating is much more complicated

High exotherm
Contaminant removal
HDN is important
Hydrogen consumption

Catalyst selection is very important

41

Reliance CNHT

MAIN

Recycle Gas

Feed

DIOS

CNHT is a classic three

reactor design

TRIM

R1

R2

Product Recycle

High pressure (63 barg)

DIOS for P control
Large product recycle for T
control
Quenching with gas
Trim reactor for Recombinant
Mercaptans

R3

Hydrotreated
Naphtha

Reformer Quality Product

S & N < 0.5 ppmwt

42

Reliance LNUU
Recycle Gas
Feed

DIOS

R3

MAIN 1

MAIN 2

R1

R2

Product Recycle

43

LNUU is an atypical design

Designed for Olefin reduction

Lower pressure (30 barg)
DIOS for P control
Quench with DIOS product
for T control

Petrochemical Naphtha
Hydrotreated
Product
Naphtha
S < 10 ppm, Br < 1
Low levels of Recombinant
Mercaptans can be allowed so
no trim reactor

Reliance LNUU vs CNHT

Advantages of the LNUU design
By using feed quench the product recycle can be reduced
This allows a lower design pressure for the same ppH2
No gas quench so lower recycle gas rate

Disadvantages of the LNUU design

DIOS product needs to be full vapor to allow feed split control
Dry point in DIOS can give rise to pressure drop
More complex optimization (feed split, max T, Si/As management)

The LNUU is not designed to make reformer feed

44

DIOS Operation

Diolefins are very reactive

DIOS operating temperatures 170C < T < 220C

RIT set by the T

Approximately 15C temperature rise is sufficient to get 70% diolefin saturation
Increase RIT only when the observed T drops below 10C

If the DIOS RIT is too high, olefin saturation can start

Temperature runaway
Recommended maximum ROT 220C

Contaminant pickup is incomplete

Temperatures are too low for the catalysts to reach Si saturation
Typically only 50% of the catalyst Si capacity is used
Temperatures are too low for As removal

45

Main RX Operation

Minimum RIT > 240C

Below this temperature olefin saturation becomes (too) composition dependent
With feed quality fluctuations olefin saturation may or may not start/complete
Large unpredictable swings in ROT

For LNUU style units

Minimize product recycle to keep acceptable T in the first RX; typically 70C
Low product recycle increases ppH2 and lowers overall LHSV
Lowest possible product recycle is a function of the feed bromine number
RX1 product will act as heat sink in RX2

Deactivation by coke formation is very low at typical operating conditions

Cycle length determined by contaminants (Si, As) and P

46

Trim RX Operation
Recombinant Mercaptans react very easily
Low operating temperature; typically 280C-300C
High LHSV; typically 10 h-1
Very low deactivation rates

47

Coker Naphtha Unit Operations

Avoid reactor temperatures between 220C (DIOS) and
240C (Main RX)
Olefin saturation becomes very feed quality dependent in this
temperature window
Can give instabilities in operation

CNHT type 3 reactor unit

Should always work

LNUU style unit

Significant cost saving in lower design pressure
More complex operation
48