conference06-21nippon ketjen resid hdm

8/16/2019 Conference06-21Nippon Ketjen Resid HDM

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4 Years Contribution to

Sustainable Petroleum Refining







The pursuit of efficiency inResid HT operation based on

investigation of feed properties

and use of newly developed

KFR catalysts

At 2011 J-C-K Petroleum

Technology Congress

Feb 22-23, 2011

Nippon Ketjen Co., Ltd.


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2

Contents

1. Introduction

2. Reactivity of VR and heavy AR feedstock

3. Introduction of newly developed KFR catalysts4. Conclusion


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3

1. Introduction

Issues related to Resid hydrotreating are as follows.- Decrease of demand for fuel oil

- Crude oil is becoming heavier and more diverse

- Treatment of non-conventional crude oil will beneeded

To cope with the above issues, we present the following.

- Investigation of a number of feed properties and theirimpact on HDS reactivity

- Newly developed catalysts for a more efficient

operation


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2. Reactivity of VR and heavy AR feedstock


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Evaluate HDS reactivity for 10 types of different oils(VR, AR, DAO)

Investigate the relation between HDS activity and feedproperties

Comparison of reactivity under high pressure

18MPa）

andmedium pressure 14MPa）

Investigate the relation between HDS reactivity and themolecular structure of the n-C7 insoluble fraction

Specify convenient feed properties that can be used forselecting crude source and adjusting operation conditions

Objectives


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Catalyst systemHDM zone KFR 23/KFR 22/KFR 20

HDS zone KFR 53/KFR 50/KFR 70

Pilot test conditions

ppH2 : 14MPa 18MPa

H2 /Oil : 1000NL/L

LHSV : 0.2h-1

Operation targetProduct Sulfur ： 0.3wt% and 0.5wt% in

DSAR(360oC+)

Catalyst system and conditions


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Feedstock

VR 10 typesOrigin： Iranian Light, Upper Zakum, Qatar Marine,

Canadian Heavy, Maya/Isthmus, North Sea main

AR 8 types

Origin: Arabian Heavy, Arabian Extra Light,

Kuwait main

DAO 1 type


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HDS reactivity under high pressure

(18MPa)

In general, the higher the sulfur content in the feedstock, the higher the

required reaction temperature for HDS. The magnitude of the increase

for VR is different from that for AR.

@18MPa-40

-30

-20

-10

+0

+10

+20

+30

1 2 3 4 5 6Sulfur in feed , wt%

T e m p e r a t u r e r e q u i r e d ,

o C AR

VR

@18MPa

Base


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The HDS reactivity of the feed correlates relatively strongly with specific

gravity, CCR content, metal content and Log（log Vis.）of the feed.

HDS reactivity under high pressure

(18MPa)

-40

-30

-20

-10

+0

+10

+20

+30

0.92 0.94 0.96 0.98 1.00 1.02 1.04 1.06Density of feed , g/ml at 15

oC


o C

AR

VR

-40

-30

-20

-10

+0

+10

+20

+30

0 5 10 15 20 25 30CCR in feed , wt%

T e m p

e r a t u r e r e q u i r e d , o

C AR

VR

Base Base

@18MPa@18MPa


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The influence of pressure on HDS reactivity were evaluated under high

pressure (18MPa) and low pressure (14MPa).

Effect of pressure

-40

-30

-20

-10

+0

+10

+20

+30

1 2 3 4 5 6Sulfur in feed , wt%

T e m p e r a t u r e r e q u i r e d , o

C18MPa

-40

-30

-20

-10

+0

+10

+20

+30

1 2 3 4 5 6 7Sulfur in feed , wt%

T e m p e r a t u r e r e q u i r e d , o

C14MPa

Base Base

DAO）


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Effect of pressure

-40

-30

-20

-10

+0

+10

+20

+30


T e m p e

r a t u r e r e q u i r e d ,

o C 14MPa

18MPa

Ref.

DAO）

Base

The difference in HDS reactivity between a certain oil and reference

feed was almost independent of pressure.


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Factors to affect HDS reactivity

Comparison of feed reactivity from the followingperspective:

- Feeds of markedly different reactivity, but with similar

sulfur content

After separation by n-C7 solubility, the insoluble fraction

（ Asphaltene） and soluble fraction (Maltene) wereinvestigated individually for their

- HDS conversion

- Averaged molecular structure

Soluble Insoluble Maltene）

Asphaltene）

Separation by heptane

Feed or Product oil


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Feeds with similar S content

-40

-30

-20

-10

+0

+10

+20

+30


T e m p e r a t u r e

r e q u i r e d ,

o C 14MPa

18MPa


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Comparison of high S vs low S feed

Comparing several types of feeds with

similar sulfur content, the less reactive

feeds contain higher amounts of sulfur

in the Asphaltene fraction.

-40

-30

-20

-10

+0

+10

+20

+30


T e m p e

r a t u r e r e q u i r e d ,

o C 14MPa18MPa

Base

0.0

0.5

1.0

1.5

2.0

Feed Sulfur in DSAR

=0.5wt%

Sulfur in DSAR

=0.3wt%

S u l f u r c o n t e n t , w t % Sulfur from MAL

Sulfur from ASP2.5

3.0

0.0

0.5

1.0

1.5

2.0

Feed Sulfur in DSAR

=0.5wt%

Sulfur in DSAR

=0.3wt%

S u l f u r c o n t e n t , w t %

Sulfur from MAL

Sulfur from ASP2.5

3.0


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Typical molecular structure of

Asphaltenes

-40

-30

-20

-10

+0

+10

+20

+30


T e m p e r a t u r

e r e q u i r e d ,

o C 14MPa

18MPa

Base


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-40

-30

-20

-10

+0

+10

+20

+30

1 2 3 4 5 6 7

Sulfur in feed , wt%


o C 14MPa

18MPa

Comparing several types of feeds of similar sulfur content, HDS reactivity

differed with the aromaticity factor of the Asphaltene molecule (fa). A higher

aromaticity factor resulted in a lower reactivity feed.

S

OH

S

N

C10H21

OH

High f a

Low f a

Typical molecular structure of

Asphaltenes


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Estimation of reactivity

from analyses

The aromaticity factors f a has a clear correlation with the amount of saturates.

The HDS reactivity has a strong correlation with the amount of saturates.

The amount of saturates can be measured easily and it can be used to

determine the HDS reactivity of the feed.

0

0.1

0.2

0.3

0.4

0.5

0 5 10 15 20 25 30Saturate in feed , wt%

f a , -

14MPa

18MPa

-40

-30

-20

-10

0

10

20

30

0 5 10 15 20 25 30Saturate in feed , wt%


o C AR

VR

Base


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The HDS reactivity of the feed correlates relatively strongly

with sulfur content, metals content, specific gravity, CCRcontent and Log（log Vis）of the feed

The HDS reactivity difference between a certain oil and thereference feed is almost independent of pressure (18MPa or14MPa)

Higher sulfur removal requires removing the S from Asphaltenes. The HDS reactivity is affected either by thefeed aromaticity factor or by how bulky the feed Asphaltenemolecules are

The amount of saturates can be used to determine the HDSreactivity of the feed.

Reactivity of VR and heavy AR


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3. Introduction of newly developed KFR grades3.1 New HDM catalyst, KFR 15

3.2 New HDS catalyst, KFR 93

3.3 KFR grades

3.4 Simulated performance of a system using KFR 15

and KFR 93


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3.1 Introduction of new HDM

catalyst KFR 15

New support technology enabled optimization of pore

structure with higher pore volume

-Improved diffusivity of metal-containing large molecules

-Improved metal capture capability

Optimized surface activity

-Effective to suppress dehydrogenation reaction at

relatively higher reaction temperature after middle of run


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KFR 15 shows higher HDM performance than KFR 23 from start of run.

With its higher metals pickup capacity the catalyst however showed an

even more prominent advantage after middle of run.

80

90

100

110

120

130

140

0 10 20 30

Metal on Catalyst, g/100ml Catalyst

H D M R

V A

KFR 23KFR 15

Test Conditions:

Temp. , oC 360 - 405ppH2 , MPa 18

H2 /Oil , NL/L 800

LHSV , h-1 1.0 - 3.0

Feedstock Properties:Sulfur , wt% 4.1Ni+V , ppm 100

Density , g/cm3 0.977

HDM performance of KFR15


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3.2 Introduction of new HDS

catalyst KFR 93

With using commercially proven support technology, both

type of active metals and their metal loadings were

optimized. We commercialized a high HDS activity

catalyst, KFR 93, which outperforms all currently available

commercial HDS catalysts.

KFR 93 exhibits unparalleled HDS activity in case the

HDM section can satisfactorily reduce metals to the HDS

section.


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HDS performance of KFR 93

KFR 93 exhibited over 10 oC HDS advantage over KFR 70 with equivalent

stability.

340

350

360

370

380

390

400

410420

0 50 100 150 200 250 300

Days on stream

N o r m

a l i z e d W A T f o r H D S , o

C

KFR 70

KFR 93

Base

+20

+40

-20

-40

Days on stream

0 50 100 150 200 250 300

Test Conditions :ppH2, MPa 17

LHSV, h-1 0.32

Target Sulfur, wt% 0.3

Feedstock Properties :

Demet. Feed of AR/VR=70/30vol%

Sulfur, wt% 1.4Ni+V, ppm 18


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3.3 KFR grades

KG 55 Ring shaped catalyst, Capture large-size scale

KF 542 Macaroni-shaped ring catalyst, Capture middle-size scale

KG 1 Ball shaped porus catalyst, Capture fine scale and iron

KG 5 Quadralobe catalyst with HDM, For size-grading

KFR 12HDM catalyst, mainly for low-mid pressure

（

15MPa）

, with higher

coke resistance based on KFR 20

KFR 20High HDM activity catalyst with HDS function, mainly for low-mid

pressure（

15MPa）

KFR 15

Newly developed HDM catalyst, mainly for high pressure

（

15MPa）

, with improved metal tolerance and coke resistance from

KFR 22/23

KFR 23

HDM catalyst, mainly for high pressure （

15MPa）

, with higher

metal resistance based on KFR 22

KFR 22High HDM activity catalyst with HDS function, mainly for high

pressure（

15MPa）

Guard

Catalysts

HDM

Catalysts


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3.3 KFR grades

HDM/HDS

Catalysts KFR 33Transtion catalyst of HDM and HDS functions, with relatively high

metal tolerance

KFR 53 HDS catalyst with relatively high metal tolerance

KFR 50 High HDS and HDN activity catalyst

KFR 50S Improved KFR 50 with higher HDS, HDN and HDCCR activity

KFR 70 Finishing catalyst with very high HDS, HDN and HDCCR activity

KFR 70B/71BImproved KFR 70 with higher HDS, HDN and HDCCR for paraffinic

AR

KFR 93Finishing catalyst with extremely high HDS, HDN and HDCCR

activity

HDS

Catalysts

Since the first commercial introduction in 1987, KFR catalysts have been

employed in 26 units with over 100 runs World Wide.


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KFR 22

KFR 23

KFR 12

KFR 20KFR 33

KFR 53

KFR 50

KFR 50S KFR 70

KFR 70B/71

HDS Activity

M

e t a l C a p a c i t y

Schematic display of KFR activity

Only the sophisticated combination of high performance catalysts can fully meet a

unit requirement.

We are now expanding our versatile and balanced HDM/HDS system by further

improvement of the HDM activity/metal tolerance with KFR 15 and by adding

extremely high HDS activity with KFR 93.

KFR 15

KFR 93


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3.4 Simulated performance of

a new system with KFR 15 and KFR 93

Performance of a new system with KFR 15 and KFR 93 was simulated,

and was compared with current KFR 23/22 and KFR 70.

Catalyst system

Replace KFR 23/22 by

KFR 15

Replace latter half ofKFR 70 by KFR 93

System A System B

Reference System New SystemHDM

KFR 33

HDS KFR 70

KFR 93KFR 70

Transition KFR 33

KFR 15KFR 23

KFR 22


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Performance of new system

Simulation indicated that the new system B with KFR 15 and KFR 93 can

lower around 2oC of WAT after MOR compared to system A.

-10

-5

0

5

10

15

20

0 50 100 150 200 250 300 350

Days on Stream, day

O p e r a t i o n

W A T ,

o C

System-A

System-B(New)

Base

+10

+20

-10

Operation Conditions : Feedstock Properties :

LHSV, h-1 0.15 Sulfur, wt% 4.4

ppH2, MPa 18 Ni+V, ppm 95

Target Sulfur, wt% 0.3 Density, g/cm3 0.995


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Performance of new system

The new system B with KFR 15 and KFR 93 can reduce metals in product

from 6 to 4ppm at SOR and 9 to 7ppm at EOR, and the difference of metalcontent between system A and B is 2ppm through the run at constant product

sulfur. It is expected that system B can reduce FCC catalyst consumption by

70-80% of system A.

0

2

4

6

8

10

0 50 100 150 200 250 300 350

Days on Stream, day

N i + V C o n t e n t , p p m

System-A

System-B(New)


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4. Conclusion

HDS reactivity of feedstock are related to the molecular

structure of Asphaltenes. More bulky structure and higheraromaticity leads to less reactivity of the feed. The amount ofsaturates can indicate HDS reactivity of the feed.

We commercialized a new HDM catalyst KFR 15 and a new

HDS catalyst KFR 93. Employing these catalysts, therequired temperature for operation can be lowered, oralternatively, the product metals can be reduced at constantproduct sulfur.

Nippon Ketjen is committed to providing optimal catalystsystems to its customers.

conference06-21nippon ketjen resid hdm

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