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2015
ptq
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catalysis
ptq
Vol 13 No 2
2015
2008
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Editor
Ren G Gonzalez
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Ren G Gonzalez
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Catalysis 2015
pcs myth.indd 1
8/3/12 09:55:39
catalysis q&a
Q
The Reid vapour pressure (RVP) of gasoline is primarily determined by the amount of light hydrocarbons
(C4s and C5s) present in the gasoline. RVP declines as
molecular weight increases. For example, the pure
component RVP of n-butane is 52 psi, the pure component RVP of n-pentane is 15 psi, and the pure
component RVP of n-hexane is 5 psi. The quantity of
C4s in gasoline has a greater effect on RVP than the
quantity of C5s. Modifying the FCC catalyst by changing equilibrium unit cell size and other properties can
shift the relative proportions of the hydrocarbon
species present in the FCC gasoline and thus shift the
RVP.
Any consideration of gasoline RVP must take into
account the entire gasoline pool of the refinery and the
unit operations that are used to produce the gasoline.
When a low RVP gasoline is desired to meet government RVP requirements, it is preferable to take C4s out
of the FCC gasoline pool and use alkylation to transform isobutane and butenes into high octane, low
vapour pressure alkylate. To reduce RVP, refineries
should optimise debutaniser operation to minimise the
C4s present in the FCC gasoline and thus maximise C4s
sent to the alkylation unit. Complexes with sufficient
alkylation capacity should also examine opportunities
to maximise butylene production from the FCC. This
can be done via proper choice of FCC catalyst and
additives.
Catalysts with lower hydrogen transfer will produce
more butylene. ZSM-5 additives and specialised dual
zeolite catalyst technologies can also increase the
amount of butylene produced. Multiple objectives
must be met in FCC operation and careful consideration of operating objectives and unit constraints is
needed when selecting a catalyst to meet a desired
goal such as optimising RVP.
Working closely with the technical service team of an
experienced FCC catalyst supplier is essential in identifying the best catalyst choice to meet refinery
objectives. An example of the application of optimised
catalyst technology to improve the properties of the
overall gasoline pool can be found in the article Role of
FCC catalyst in refinery profitability, PTQ, Q1 2014 by I
Chavdarov, D Stratiev, I Shishkova, R. Dinkov, V
Jegorov and P Petkov.
www.eptq.com
Catalysis 2015 5
6 Catalysis 2015
www.eptq.com
Nasty Stuff
pcs nasty.indd 1
1/6/12 11:58:35
8 Catalysis 2015
Rive
For conventional FCC units trying to maximise propylene output, most refiners will use a catalyst having
relatively low levels of rare earth exchange. This lower
unit cell size E-cat will inhibit hydrogen transfer reactions, which will increase yields of LPG olefins.
Additionally, many refiners will implement a ZSM-5
additive in order to further raise propylene yield.
ZSM-5 preferentially cracks the lower octane olefin
components in the C7C10 gasoline range into lighter
olefins in the C2C5 range, primarily propylene.
Rive Technology (Rive) has developed and commercialised Molecular Highway technology whereby a
precise series of mesopores are engineered into Y
zeolite, the primary active component of all FCC catalysts. These mesopores promote improved diffusion of
FCC feed molecules into and out of the zeolite crystals
of the FCC catalyst.
In addition to decreasing formation of coke,
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bottoms and dry gas, Rive has commercially demonstrated its ability to increase propylene production for
a given set of operating conditions. These valuable,
reactive molecules are quickly and efficiently channelled through the mesopores of the zeolite instead of
succumbing to secondary and tertiary cracking reactions, which would turn them into LPG paraffins and
dry gas.
Even larger propylene gains can be achieved for
refiners utilising the ZSM-5 additive, alongside a Rive
FCC catalyst. Because Rive also preserves the olefinicity of the gasoline range molecules, the combined
system of Rive catalyst with the ZSM-5 additive has
shown dramatic increases in propylene yield.
When the ZSM-5 additive is not used, switching to a
Rive catalyst typically increases the absolute propylene
yield by nearly 1 wt%. When the ZSM-5 additive is
used, switching to a Rive catalyst typically increases
the absolute propylene yield by nearly 2 wt% (all
values derived from ACE testing at constant 75 wt%
conversion).
10 Catalysis 2015
www.eptq.com
Practical
Elegance
LL-ElegantPracticality.indd 1
1/19/15 3:02 PM
12 Catalysis 2015
www.eptq.com
choose
wisely.
At CRI, we provide catalyst and process solutions tailored for the
petrochemical and refining industry. Our technology is an integral part in
helping achieve success in a customer's application. Our strengths in R&D,
catalyst manufacturing and technical service allow CRI to progress quickly
from lab scale to production to customer results. We pride ourselves on
developing lasting relationships with our customers through collaboration
and successful implementation of catalytic solutions.
It is all part of our commitment to delivering innovation.
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dilution and solvent dewaxing processing all involve dewaxing catalyst; for existing units a revamp is
high capital costs and margin erosion due to significant required. The primary advantage of noble metal
diesel yield loss. Catalytic dewaxing provides a dewaxing catalysts is the much higher isomerisation
competitive economic alternative to reduce the impact selectivity, leading to minimum loss of diesel yield to
of these strategies.
light gases and naphtha.
The general principle behind catalytic dewaxing
Unfortunately the best approach to catalytic dewaxis to employ a catalyst with functionality to initiate ing is a very complex question whose answer depends
a combination of hydrogenation, hydrocracking upon the degree of desired cold flow improvement,
and/or isomerisation reactions to either reduce paraf- available unit hardware (reactors, beds, quenches,
fin chain lengths or to rearrange the chains to produce internals), unit revamp feasibility, hydroprocessing
lower melting point isoparaffins. There are objectives/constraints and the particular set of
two commonly employed solutions for catalytic economics for your unit. Fortunately, catalyst vendors
dewaxing, either a single stage flow scheme that and technology licensors have proprietary unit perforemploys a base metal dewaxing catalyst or a two stage mance and economic evaluation tools at their disposal
flow scheme that employs a noble metal dewaxing to assist you in evaluating your unit and its
catalyst.
specific circumstances.
The single stage solution is
the least capital intensive solution because it involves the use
of a base metal dewaxing catalyst layer at an optimal location
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PREMIERE INTEGRATED
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DOWNSTREAM EVENT
metal dewaxing catalysts have
historically been designed with
small pore diameters to selectively diffuse paraffins into the
catalyst pill while preventing
diffusion
of
isoparaffin,
napthenic and aromatic constituents. The diffused paraffins
are then exposed to zeolitic
based active sites where they
are cracked and/or isomerised
to form smaller chain paraffins
200+
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tages of base metal dewaxing
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catalysts as opposed to noble
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Catalysis 2015 15
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Catalysis 2015 17
14.5
1% REO
3% REO
5% REO
Aromatics, ff wt%
14.0
13.5
13.0
12.5
12.0
11.5
10
15
20
25
30
ZSM-5, wt%
Figure 1 Gasoline aromatics on feed basis at 71 wt% conversion for base catalysts
containing 1 , 3 and 5 wt% RE2O3. The base catalysts are tested with 5 and 25 wt%
ZSM-5 additive added and as-is
18
Catalysis 2015
www.eptq.com
www.eptq.com
Naphthenics + aromatics,
ff wt%
18.5
1% REO
3% REO
5% REO
18.0
17.5
17.0
16.5
16.0
15.5
10
15
20
25
30
14
1% REO
3% REO
5% REO
13
12
C3=, wt%
11
10
9
8
7
6
5
4
10
15
20
25
30
14
1% REO
3% REO
5% REO
13
12
11
C4=, wt%
10
9
8
7
6
5
4
10
15
20
25
30
Catalysis 2015 19
$ WIN $
C6
C3
C8
C7
C4
C3
C3
C5
START
C4
C4
C3 and C4 olefins
Beta scission
Gasoline range
molecules
Olefin
isomerisation
Conclusions
Diesel range
molecules
Olefins
oligomerisation
Aromatic
transalkylation
Olefin
aromatisation
Figure 5 Reaction pathways over ZSM-5 in the FCC unit. ZSM-5 catalyses many more
reactions in the FCC than only cracking of olefins
characteristics of the base cracking catalysts
and feedstocks., Ind. Eng. Chem. Res., 1999,
3854-3859.
7 Adewuyi Y G, Klocke D J, Buchanan J S,
Effects of high-level additions of ZSM-5 to a
fluid catalytic cracking (FCC) RE-USY catalyst,
Appl. Catal. A: Gen., 131, 1995, 121-133.
8 Buchanan J S, Adewuyi Y G, Effects of high
temperature and high ZSM-5 additive level on
FCC olefins yields and gasoline composition,
Appl. Catal. A: Gen., 134, 1996, 247-262.
Bart de Graaf is FCC R&D Director with
Johnson Matthey Process Technologies, Inc. He
holds an MSc in chemical engineering and a
PhD in heterogeneous catalysis and chemical
processes. Email: Bart.deGraaf@matthey.com
Mehdi Allahverdi is FCC Applications Manager
with Johnson Matthey Process Technologies,
Inc., Savannah, Georgia, US. He holds a
PhD in materials science and engineering
Gasoline range
molecules
Crack on RE-USY
E-USY
Aromatic
transalkylation
Olefin
aromatisation
nsfe
f r:
fe
r
Hydrogen Transfer:
olefin to paraffin
naphthene to aromatic
Ol fi
f / lil
Olefins/oligomers
Olefin
isomerisation
Figure 6 Y-sieve and ZSM-5 both catalyse many reactions of gasoline (and LPG, see Figure 5) range molecules. The relative ratio
between both zeolites will determine the composition and yields of gasoline and LPG
www.eptq.com
Catalysis 2015 21
cattec.indd 1
26/02/2013 16:59
ZSM-5 chemistry
www.eptq.com
3.0
Base
Base + 15% ZSM-5
Base + 30% ZSM-5
Base + 50% ZSM-5
2.5
2.0
1.5
1.0
0.5
0
10
11
Carbon number
Figure 1 The amount of light olefins in naphtha at different ZSM-5 loadings. The
challenge is how to convert the remaining C6 and C7 olefins to C3 and C4 olefins
Catalysis 2015 23
16
ZSM-5 (with P)
ZSM-5 (no P)
FCC
Propylene yield,
wt% at 70% conversion
14
12
~8%
10
8
~4%
6
4
2
0
FCC
FCC + ZSM-5
(no P)
FCC + ZSM-5
(with P)
16
14
12
10
8
6
4
2
0
10
20
30
40
50
60
70
80
90
100
Ethylene
Propylene
C3=/C2=
Butenes
Propane
Total C2Gasoline
Coke
Acty@ c/o=7.7
Fresh
without P
4.2
8.6
2.0
6.7
8.9
6.2
29.8
3.2
1.83
Steamed
without P
0.9
9.4
10.9
10.3
1.0
1.9
39.3
3.2
1.57
Fresh
with P
4.2
12.7
3.1
10.4
3.8
5.4
29.5
2.2
1.99
Steamed
with P
2.1
13.7
6.5
12.2
1.5
3.1
33.2
2.1
2.03
*ACE cracking data @ 70% conversion for a mixture of 76.5 wt% of 1 wt% REO FCC catalyst and 23.5 wt% of
MOA ZSM-5 additive. Steam deactivation conditions: 15h/1500F/100% steam.
Table 1
24 Catalysis 2015
www.eptq.com
www.eptq.com
16
14
12
10
8
6
4
2
0
10
20
30
40
50
15.0
12.5
10.0
7.5
5.0
10
15
20
25
15.0
12.5
10.0
7.5
5.0
10
15
20
25
Catalysis 2015 25
Propylene, wt%
Commercial results
Actual propylene
Estimated propylene
Beginning of ZIP trial
29 Jan
26 Feb
26 Mar
23 Apr
21 May
Actual propylene
Estimated propylene
Beginning of ZIP trial
19 Apr
17 May
14 Jan
12 Jul
Figure 7 ZIP produces a similar propylene yield using less ZSM-5 additive
Propylene, wt%
BASF ZIP
BASF MOA
0.89
0.90
0.91
0.92
0.93
0.94
0.95
26
Catalysis 2015
Conclusion
www.eptq.com
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06.12.2013 10:17:28
Catalysis 2015 27
www.exxonmobil.com/tsl
FP.LubesAd_4PTQ.indd 1
2/13/15 9:04 AM
he process of optimising a
catalyst is no easy task. A few
of the keys to success are
designing the proper pore size
distribution into the catalyst, optimising the metals composition and
maximising utilisation of the
metals. Extensive work has been
completed to define the optimum
pore architecture of catalysts for
processing heavy feeds.
Figure 1 compares the relative
activity of different catalyst preparations as a function of increasing
catalyst pore size. The pore size
and surface area of a catalyst are
dependent variables, meaning that
as the pore size increases, the
surface area decreases, and thus the
number of active sites decreases.
On the left side of Figure 1, the
catalysts have a high surface area,
but the pores are too small to allow
large VGO molecules access to the
active sites. On the right side of the
figure, the pores are very large and
allow easy access, but the surface
area (and thus the number of active
115
Decreasing
pore size
Increasing
pore size
Relative activity
120
100
90
80
115
100
90
80
70
Relative activity
130
60
70
50
60
Decreasing access to active sites
www.eptq.com
Catalysis 2015 29
170
Relative activity
160
150
140
130
120
110
100
90
130
125
586DX
AT575
120
115
110
105
100
95
90
HDS
HDN
190
180
170
160
150
140
130
120
110
100
90
80
70
HDS
HDN
AT775
AT792
AT795
486DX
30
Catalysis 2015
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hydroprocessing
catalysts offering
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190
180
170
160
150
140
130
120
110
100
90
80
70
HDS
HDN
AT775
AT792
AT795
486DX
25
Activity advantage, F
20
HDS
HDN
15
10
5
0
AT575 / AT795
586DX / 486DX
Conclusion
Catalysis 2015 33
relentless
2/18/15 9:47 AM
www.eptq.com
Sampling is a series
of processes used
by precious metals
refiners to create a
homogeneous mass
from spent catalyst
lots
After a batch of spent precious
metal-bearing catalysts is homogenised and a representative sample
drawn, a series of laboratory instrument
analysis
procedures
is
conducted, commonly known as
assaying. Sampling is a series of
processes used by precious metals
refiners to create a homogeneous
mass from spent catalyst lots which
are randomly sampled in order to
determine the type and percentage
of precious metals remaining in the
entire lot. However, in cases where
the lot size is large (as it usually is
Pyrometallurgical vs
hydrometallurgical processing
Catalysis 2015 35
36
Catalysis 2015
Quality precious
metals recovery and
refining requires
skilled people,
sophisticated
equipment and many
years experience
settlements are delayed, and the
catalyst owner may have to finance
replacement metals for new catalyst
to ensure a seamless process flow.
Quality precious metals recovery and refining requires skilled
people, sophisticated equipment
and many years experience to
complete the full cycle and arrive at
accurate
(and
agreed
upon)
samples that are used to determine
actual precious metals content in a
spent catalyst lot.
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Finding and
working with the
right refiner can
make a significant
difference in returns,
thus enhancing
overall corporate
profitability
Enhancing corporate profitability
Conclusion
Catalysis 2015 37
breakthrough
catalyst
technology
Johnson Mattheys new breakthrough catalyst technology, CATACELJM SSR, a
high performance catalyst coated stackable structured reactor for steam
reforming, delivers greater capacity and longer catalyst life than traditional
pelleted catalysts.
Our CATACELJM SSR technology is proven to ease operating limits on the reformer
and increase throughput through reduced tube wall temperature, lower pressure
drop, decreased energy consumption, and improved carbon resistance.
Our technical support team will work with you to
assess your needs and determine if
CATACELJM SSR technology is a good
fit for your operation.
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lower)
pressure
drop
when
compared to traditional catalyst
pellets. In addition, the fans offer
1.5 to 2.0 times more geometric
surface area than conventional
pellets.
Catalysis 2015 39
Pressure drop
Katalco GQ series
Catacel SSR
Mass flow
Katalco GQ series
Catacel SSR
Mass flow
Figure 6 Heat transfer vs flow
Relative performance
indicator
Activity
Heat transfer
Pressure drop
Rings
4-Hole
Quadralobe
Catacel SSR
Catalyst type
Figure 7 Relative performance of various steam reforming catalysts
40
Catalysis 2015
www.eptq.com
www.eptq.com
Furnace temperature, C
940
920
900
880
860
840
820
800
300
Pellets
SSR
400
500
600
700
H2 production, Nm3/hr
Case studies
120
110
100
90
80
70
60
50
40
30
20
10
0
300
Pellets
SSR
400
500
600
700
H2 production, Nm3/hr
20-30% savings in burner fuel.
Catalysis 2015 41
1
CatacelJM SSR
Same throughput
100.0
99.5
99.4
15.0
860
2.75
885
1.8
1.01
991
100.2
2
CatacelJM SSR
Additional throughput
115.0
112.5
105.0
7.5
861
2.80
891
2.1
1.28
1012
115.0
Installing SSR
catalyst can provide
a simpler and more
cost effective way
of achieving the
increased throughput
required
so that these conditions no longer
limit the reformer.
Case 2 shows that a 15% increase
in throughput can be achieved
within the existing constraints of
tube wall temperature and pressure
Cumulative
Expenditure,
Reduced
steam ratio
with SSR catalyst on a hydrogen plant reformer
expressed as
a % of total Installed Cost (TIC)
Factored off
Case
Base
Catalyst Equipment
QuadralobeJM
DescriptionFactored off
Base
Equipment
Relative gas
feed flow, %
100.0
Relative gas fuel flow, %
100.0
Relative total natural gas flow, %
100.0
Steam ratio
2.9
Pressure drop, bar
2.65
Exit temperature, C
827
Max tube temperature, C
867
Min carbon margin, C
39
Relative flue gas heat duty, %
100.0
Relative process gas heat duty, %
100.0
Relative hydrogen make, %
100.0
Table 2
42 Catalysis 2015
1
CatacelJM SSR
Same steam ratio
99.9
98.9
99.6
2.9
2.65
827
861
59
98.7
99.8
100.0
2
CataceljM SSR
Lower steam ratio
102.4
91.5
99.4
2.7
2.55
827
861
52
98.2
96.2
100.0
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Catalyst
Number tubes
Number tube rows
Number tubes/row
Tube ID, mm
Tube OD, mm
Tube wall thickness, mm
Tube heated length, m
Furnace length, m
Furnace width, m
Heat load, MW
Catalyst pressure drop, bar
Minimum tube wall margin, C
Relative cost, %
QuadralobeJM
352
2
176
108.0
132.0
12.0
13.72
36.03
2.00
134
3.31
34
100.0
CatacelJM SSR
322
2
161
111.4
132.0
10.3
14.00
32.95
2.00
134
3.31
34
90.2
Table 3
Impact of SSR catalyst on a new top fired reformer
Catalyst
Number tubes
Number tube rows
Number tubes/row
Tube ID, mm
Tube OD, mm
Tube wall thickness, mm
Tube heated length, m
Furnace length, m
Furnace width, m
Heat load, MW
Catalyst pressure drop, bar
Minimum tube wall margin, C
Relative cost, %
QuadralobeJM
728
14
52
115.0
134.4
9.70
13.18
14.96
32.52
263
2.83
79
100.0
CatacelJM SSR
636
12
53
115.6
134.4
9.40
14.25
15.22
27.94
263
2.78
79
92.0
Table 4
Conclusions
Structured SSR
technology delivers
a significant
improvement
in performance
operation over typical reforming
catalyst lives in commercial steam
reformers. Their adoption in a steam
reformer results in significantly
cooler tubes with lower methane
slip and lower pressure drop. This
can result in the easing of these
operating limits on the reformer,
Catalysis 2015 43
15MAKT033-Cap-ad-update-fnl.pdf
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MY
CY
CMY
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Properties
Maximum stability for heaviest feedstocks; demetallisation;
removal of asphaltenes and Conradson carbon residue
1.5Q, 3Q Excellent stability; lowest hydrogen consumption
1.3Q, 2Q Good stability; good hydrodenitrification (HDN) activity
1.3Q, 3Q Excellent stability; maximum direct desulphurisation (DDS)
activity; lowest hydrogen consumption
1.3Q, 2Q Good stability; high HDN activity
1.3Q, 2Q Excellent stability for VGO feeds; high HDN activity
1.3Q, 2Q Good stability; excellent HDN activity; denitrogenation
and dearomatisation
1.5Q. 2.3Q Extreme HDN and aromatic saturation activity
Table 1
Grading + demetalisation
Active catalyst
Zoning
Catalysis 2015 45
and demetalisation
Grading
Zone A: removal of metals, asphaltenes, CCR; management of heavy aromatics
Zone B: polyaromatics saturation; bulk HDS and HDN (removal of easy S and N)
atalyst
46 Catalysis 2015
In action
Conclusion
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Catalysis 2015 47
48 Catalysis 20155
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The
safe
mu
pro
fun
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