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The EURECAT Group

General Presentation

Albemarle
April 2015
Eurecat Organization & Locations

TOTAL-
Eurecat EURECAT SA Italian Saudi & Kuwaiti
Joint La Voulte/France Partners partners
Venture

AL-BILAD
PETROVAL SA EURECAT FRANCE SAS CATALYSTS Co.
Le Havre/France La Voulte/France Al-Jubail/Saudi
EURECAT US Inc. Arabia
ECO-RIGEN EURECAT INDIA
PETROVAL US Inc. Pasadena, TX/USA EURECAT-Bitterfeld,
McAlester, OK/USA S.r.L. Jhagadia/Gujurat
Deer Park, Germany
Gela/Italy India
TX/USA
Eurecat US and Canadian Refining Customers

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Eurecat Latin American Refining Customers

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Eurecat Petrochemical Customers

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Catalyst Manufacturing Customers

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Eurecat Services Portfolio

Sulfiding Spent Catalyst Management

CATALYST CATALYST
SULFIDING REGENERATION CATALYST CATALYST
& & RESALE RECYCLING
ACTIVATION REACT

Totsucat REACT for Albemarle Metals


Regenerated
and Optional catalysts to restore 95% Reclaim
Catalyst as Oxide
Passivation of original HDS activity
or Totsucat
www.Eurecat.com
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EX-SITU CATALYST SULFIDING / ACTIVATION

Totsucat = Totally Sulfided Catalyst

H2S H2O

MoO3 MoS2
H2

Water produced: around 10 wt% of catalyst weight


Exothermal reaction

The catalyst is
Activated, CATALYST
SULFIDING
&
not just ACTIVATION

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presulfided.
The Totsucat Process

Patented

Totsucat is a proprietary patented process

Carefully controlled sulfiding

Homogenous sulfiding All oxidic metal sites


are sulfided
Uses high purity H2S and H2
Samples tested every two hours to ensure that
the catalyst is adequately sulfided
Totsucat Benefits

Load-and-Go reactor startups


No exotherms
Minimal sour water formation
No additional H2 needed at startup
No H2S released
No odors
No handling of sulfiding chemicals
Catalyst performance is maximized
Upset conditions will not damage the catalyst
TOTSUCAT EX-SITU CATALYST SULFIDING /
ACTIVATION
EURECAT is different from Porocel ActiCat process:

OXIDE CATALYST
H2
-S-
+ -S-
+ heat
EX-SITU
PRESULFIDING EX-SITU
Porocel ActiCat SULFIDING & ACTIVATION
TOTSUCAT

LOADING

H2 H2
START-UP
+ -S- + heat
+ heat

START-UP
IN-SITU SULFIDING

Porocel ActiCat impregnates the catalyst


START-UP
with a sulfur-containing compound. ActiCat
still requires the standard in-situ sulfiding procedure

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Cookie Analogy

Porocel ActiCat
Still requires a sulfiding
start-up (1-3 days) to
activate the catalyst. Eurecat TOTSUCAT
Like cookie dough, it still Sulfided and Activated
requires time to cook. Catalyst Ready to Load and Go
Like these cookies, ready to
eat right out of the box
Totsucat Family

Hydrocracker Pretreat Hydrocracker

Lube HT
Gasoline HT

Cat Feed HT

DAO/Resid HT
Typical Totsucat Applications

Over 80 Million Pounds of Totsucat Pre-Activation

Critical Path Temperature Sulfur Sensitive Units Processing


Units Limited Units Units Cracked Feeds
The cost of Some units Reformers and CFP version of
downtime cannot achieve Isom units Totsucat allows
typically the temperature contain precious startups utilizing
outweighs the levels required metal catalysts cracked stocks
cost of Totsucat for sulfiding, that are sensitive
preactivation resulting in to H2S CFP = Cracked
inadequately contamination Feed Protection
sulfided catalysts No H2S release
that will not from Totsucat
perform as
designed
Startup with In-Situ Sulfiding
Liquid phase with SR Feed

Temperature (F)
Cracked
feed
750 H2S breakthrough Stop DMDS

575 DMDS Secondary Sulfiding


SR Feed
Initial SR Feed + DMDS at 175-300F
390
Sulfiding Monitor H2S at outlet
Sulfide at 600-660F
Sulfiding 3 days of SR feed
200 Drying step completed in 15-24 hrs

6 12 18 hours 3 days
Startup with In-Situ Sulfiding
Liquid phase with SR Feed H2S poisoning
downstream?
Stripper
Temperature (C) flooding? RG compressor
Cracked
failure?
Amine unit H2S feed
400
Lose
overload? Stop DMDS
H2S breakthrough induced sulfur off
H2S corrosion? the cat?
DMDS skidDMDS sampling? Secondary
300 CorrectSulfiding Catalyst
failure?
SR Feed sulfiding reduction?
Obtain/store Activation
Initial SR Feed + DMDS
temperature? at 80-150C
200 Monitor H2S at outlet
SR feed? exotherm?
Sulfiding
Sulfide at 315-350C
DMDS Sulfiding 3 days of SR feed
Enough
100 smell? Drying step
hydrogen?
Catalyst
Activation activity ???
procedure 10 20 30 hours +3 days
24h coverage?
Totsucat G Startup
Liquid phase with SR Feed

Temperature (F)
Cracked
feed
750
Straight
Run
575
feed
SR Feed introduction at low T (175-450F)
Go to Start of Run Temp in only 6-10 hours
390 SR Feed for 3-4 Days
Progressively switch to cracked feed
200 Advantages: Simple startup procedure.
No risk of event which could damage the catalyst

6 12 18 hours 3 days
Issue of Cracked Feed

Cracked Feeds contain olefins, di-olefins, and


aromatics that form gums and tars when
exposed to hyper-active sites on freshly
sulfided catalysts.

Coker naphtha
FCC naphtha
Coker gas oil
LCO (light cycle oil)
Cracked Feeds at Start-Up
Gums and tars formed
during startup
Compounds readily
deposit on catalyst surface

The deposits block catalyst


pores and active sites
Standard Procedure:
Wait 3 days after start-up Results in permanent loss
before adding cracked feed of catalytic activity
Cost of Waiting Can Be Expensive
Delaying the introduction of cracked feeds can have significant
costs:

Lost profits from processing cracked


and heavy feeds.
Not enough straight run feed for 3 days
of startup.
Storage costs for cracked feeds that
must be held for processing later.
Solution: Totsucat CFP
CFP = Cracked Feed Protection
In addition to Totsucat preactivation, Totsucat
CFP has carbon carefully deposited on the
catalyst surface
Hyper-active sites are moderated
Catalytic acidity is also reduced
Start cracked feed at 175-200oF
Benefits
Eliminate 3-days wait before starting cracked
feed
No additional SR feed storage for start-up
No cracked feed storage for 3 days
Startup with Totsucat CFP
Liquid Phase with Cracked Feed

Temperature (F)
SOR
400 Progressive
Introduction of
300
Cracked
Feed Introduce cracked feed at 175-300F
Heat up at 35F/h up to 480F
200 After 480F Heat up at 20F/h up to SOR.
Advantages: Safe fast start-up; Additional 3
to 4 days of cracked feed processed; No
100
need for SR or Cracked Feed storage

6 12 18 hours 3 days
HC and HC-PT with Totsucat
Totsucat for Hydrocrackers
Several Commercial References

UOP, Axens, & Haldor-


Topsoe HC Catalysts:
Approved for Totsucat
Hydrocracking: Totsucat with AP
(Acidity Protection)
Developed for HC Catalysts

Acidity Protection for HC Catalyst


Tempers start-up cracking activity
Eliminates ammonia handling
Ease of Start-UP

U.S. reference since Dec-2012


Totsucat Passivation
Totsucat (unpassivated) is self-heating and
requires inert loading
Quantified by CSHT (Critical Self Heating
Temperature)

Only most reactive sites are passivated


These sites (unpassivated) can start the self
heating process when exposed to air
Oxygen is chemisorbed on these sites
Reaction is reversible upon start-up
Passivationofthesesitesremovesthestarting
pointforselfheating
Totsucat Passivation

No activity or sulfur is lost

Resultingcatalystispassivatedandcanbe
loaded under air with reasonable
precautions in handling

Totsucat with passivation can be loaded


under air

Avoids inert atmosphere loading safety


issues
Loading in Air with Precautions
Preferred To Be Avoided
No chimney effect Chimney effect (e.g. open nozzles,
manways, or instrument line
purging with air)
Reactor loading with constant Unsupervised reactor loading, e.g.
supervision during night shift
Constant temperature and SO2 No temperature or SO2 monitoring
monitoring during loading
Contingency plant nitrogen No contingency nitrogen supply
supply in case of chimney effect
heating
Breathing air (SCBA) inside Loading without
reactor breathing air (SCBA)
Pressure test with nitrogen or Pressure test with air(!)
hydrogen

Eurecat offers loading and start-up assistance.


Passivation and Standard Totsucat
Left: Passivated Totsucat
Right: Standard (non-passivated) Totsucat
2 hour video compressed to 3 minutes
Both 1 liter samples in screen basket start at
72-73F
Standard Totsucat (right) begins to heat
rapidly and reaches 551F in 48 minutes
followed by a slow cool down.
Passivated (left) very slowly heats to a
maximum of 101F and then begins to cool
NiMo, CoMo, and NiW catalysts can be safely
loaded under air with Passivated Totsucat
Self-Heating Comparison for Passivation
versus Standard Totsucat
Temperature Data for Passivated versus
Standard (non-passivated) Totsucat
600
passivated non-passivated
550
Non-passivated reaches 550F
500
in 50 minutes
450
Catalyst temperature (F)

400
350
300
250
200
150
Passivated Totsucat reaches max 101F
and then begins to cool
100
50
0 50 100 150 200
Time (minutes)
Canadian NHT
Air Loading of Passivated Totsucat G

53-55F

No SO2 or H2S was detected at any time during the


loading.
Dow-Plaquemine
Air Loading of Totsucat-Activated CoMo
110,000 lbs CoMo sock loaded
Totsucat G
75oF ambient temperature

Maximum 10 F increase in catalyst temperature over


ambient.

No H2S detected SO2 below 5 ppm

Unit start-up with standard Totsucat procedures


Start SR feed and H2 then heat up to normal operating
temperatures

Start up activity as projected


Dow is happy with results and will do it again.
Petrobras-Regap
Air Loading of Totsucat-Activated CoMo
ULSD unit with 460,000 lbs CoMo dense-loaded
Totsucat D
~90oF ambient temperature

10-15oF increase in catalyst temperature over 3 days

No H2S detected

SO2 measurements below 5 ppm with one


measurement of 11 ppm

Unit start-up with standard Totsucat procedures


Start SR feed and H2 the heat up to normal operating
temperatures

Start up activity as projected


Eurecat Services Portfolio

Sulfiding Spent Catalyst Management

CATALYST CATALYST
SULFIDING REGENERATION CATALYST CATALYST
& & RESALE RECYCLING
ACTIVATION REACT

Totsucat REACT for Albemarle Metals


Regenerated
and catalysts to restore 95% Reclaim
Optional of original HDS activity Catalyst as Oxide
or Totsucat
Passivation
www.Eurecat.com
Page 34
WHAT CAN WE DO FOR YOUR:
HYDROTREATING UNITS

TOTSUCAT (Sulfiding+Activation) for fresh or regen


catalyst

Purchase, Resale, Disposal of Spent Catalyst

Regeneration / Rejuvenation of Spent Catalyst


SAS (Sample-Analyze-Segregate) bin-by-bin analysis

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Eurecat Catalyst Regeneration
Eurecat has largest regeneration
capacity in the World
4 US Regeneration Lines
2-Rotolouvres
2-Ebullated Bed
18 Regeneration Units
Worldwide

US Regeneration Plants
Pasadena, TX
McAlester, OK
REGENERABILITY STUDY

Contaminants

Catalyst Activity Testing


Carbon
for all NiMo & CoMo
Catalysts
Sulfur

Surface
Lab Area
Regenerated
catalyst
Crush Strength

Particle size
Distribution (PSD)

EURECAT provides the data and


makes recommendations
You decide whether to regenerate

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Pilot Testing Units for Activity
Eurecat pilot tests catalysts versus fresh reference to
validate the regenerability of HPC catalysts
Two 10-Reactor Pilot Test Units
Testing for Relative Pressure Drop
Pilot testing for RDP (relative pressure drop) versus
fresh catalyst reference.
Proven accuracy in multiple units
RDP testing yields factor versus fresh reference with sock or
dense loading
Actual versus Predicted Delta P
1,8
1,6
1,4
Delta P measured (bar)

1,2
1,0
0,8
0,6
0,4
0,2 Delta P measured = f(Delta P predicted) 1:1

0,0
0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4 1,6 1,8
Delta P predicted (bar)
Case 1
Reactor Dump Side view

Front view
Case #1 Side Dump

Dig out
SAS
Reactor Unloading Mock up

Case #2 2 beds dense load


transfer pipes
1 dump pipe (45)

45
Case #2

Dig out
SAS
Case #3 Side view

Front view
SAS for Regeneration

SAS = Sample Analyze Segregate

Recover clean catalyst based on analysis of


each individual bin

Not just single analysis of composite sample

Catalyst quality will vary greatly bin-by-bin


based on the dump characteristics
SAS Case Study
(Sample-Analyze-Segregate)

Standard Composite Sampling


Contamination:
As=0.03wt%
Inerts 1"
Na=0.38wt%
Inerts 1/4" Si=0.23wt%
CoMo 1/10
3 tons sock load SA=179 m2/g
RVA=89% - RWA=87% vs fresh
+ high contamination of CoMo 1/10
CoMo 1/16 (Na=3.24wt%, As=0.31wt% and Si=1.49wt%)
95 tons dense
load

Summary:
Ballls 1/4"
Low activity (89%) with As and Si
Balls 1"
SAS Case Study SAS bin by bin Analysis
(Sample-Analyze-Segregate) Na (wt%)
As (wt%) %As %Na %Si Si (wt%)
0.30 1.80

0.25 1.50

0.20 1.20

I nerts1" 0.15 0.90


Inerts1/4"
CoMo 1/10 Standard sampling 0.10 0.60
3 tons sock load
Contamination:
As=0.03wt% 0.05 0.30

CoMo 1/16
Na=0.38wt% 0.00 0.00

95 tons dense Si=0.23wt%


0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75

load Bins number

SA=179 m2/g
RVA=89% - RWA=87% vs fresh
Billes 1/4"
+ high contamination of CoMo 1/10
Billes 1" (Na=3.24wt%, As=0.31wt% and Si=1.49wt%)
SAS Case Study
(Sample-Analyze-Segregate)
Standard composite sampling procedure:
95T of catalyst out of Customer specifications
Low RVA (89% vs fresh)
Na and As contamination

209,000 lbs CoMo 1/16 for recycling


SAS Bin-by-Bin sampling procedure:
160,000 lbs of catalyst within customer specifications
Excellent RVA (97% vs fresh)
Low metals contamination

160,000 lbs for regeneration


Only 49,000 lbs for metals recycling
SPENT CATALYST PURCHASE BY EURECAT

Whats in it for you :

- Sell your spent catalyst to Eurecat!


- Spent catalyst disposal becomes a profit instead of merely a cost
- Eurecat will take all of the spent catalyst
- Regenerate and resell the good catalyst
- Recycle the remaining catalyst through metals reclamation

- Refiner can evaluate the regenerated catalyst with first right to repurchase

- All starts with a reactor loading diagram!

CATALYST
RESALE

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CATALYST RESALE

Whats in it for you :

- 60% reduction in catalyst expense budget

- Very fast delivery from stock (Pasadena, TX and McAlester, OK)


In-house logistical services road, maritime, air

- Rigorous quality control / activity testing

Activity Testing for CoMo catalysts

NiMo Testing Planned for 2014

- Large resale catalyst portfolio


Worldwide pool of many different catalysts; focus on latest generation types.

CATALYST
RESALE

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CATALYST RESALE

How does it work :

Sales:
- Portfolio, techno-commercial details and samples can be provided at any time.
- Any catalyst not readily available will be sourced within worldwide pool.
- Catalyst lots are activity tested.
- We can arrange packaging, sulfiding and transport to your site.

Consignment resale:
- You wish to get rid of a catalyst that is worth more as a catalyst than its
contained molybdenum.
- We will market it for resale within the worldwide pool.
- Upfront cost can be minimized by postponing regeneration.

CATALYST
RESALE

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WHAT CAN WE DO FOR YOUR:
C4 OR C5/C6 ISOM

Stripping/carbon burn-off &


dechlorination for metals recovery


Carbon burn-off for metals recovery


Regeneration/(chlorination) for reuse

Category: Catalysts:

Pt/mordenite I-7, HS-10, HS-12, Z-700, OK OK -


Hysopar

Pt/Cl2/alumina I-8, I-80, I-82, I-83, I-12, - - OK


I-120, ATIS-xL, AT-xx

Pt/Cl2/alumina IS-612, IS-614 OK - OK

Zr-based LPI-100, PI-242 OK OK -

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WHAT CAN WE DO FOR YOUR:
SELECTIVE HYDROGENATION UNIT

Pd catalysts:
Reactivation
Reduction (fresh catalyst)
Stripping (for metals recovery)

Ni catalysts:
Regeneration
Selectivation and reduction (fresh and
regenerated)
Recycling (destruction)

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THANK
YOU

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