Originally appeared in:

July 2013, pgs 67-69.

Used with permission.

Special Report Refinery of the Future

R. A. RAKOCZY and P. M. MORSE,
Clariant, Munich, Germany

Consider catalytic dewaxing as a tool

to improve diesel cold-flow properties
Diesel engines rely on effective dispersion of fuel to ensure behavior (cetane number and heating value), viscosity and flow
efficient combustion. In cold weather regions, maintaining behavior specifications are important performance factors for
the fluidity flow of fuels can be difficult. Catalytic dewaxing is diesel fuels. The top four globally standardized properties are:
a selective hydrocracking process that provides a valuable im- VI
provement to low temperature performance of middle distillate PP
feedstocks. It greatly improves cloud point (CP) and cold-filter CP
plugging point (CFPP) properties of diesel fuels. CFPP.
Whereas VI and PP primarily describe the quality of the mid-
Background. At present, most US refineries are optimized for dle-distillate fluidic behavior and its ability to be transported from
the production of gasoline, i.e., fluid catalytic cracking (FCC) tank to engine, CP and PP describe the ability to filter and dis-
units. With the growing interest in diesel-powered passenger perse the fuel at lower temperatures. The VI is calculated by the
cars, existing refineries will not be able to serve that new de- kinematic viscosity at 40C (100F) and 60C (140F). At higher
mand for clean diesel. Investments in new technologies to pro- VIs, the change of kinematic viscosity with temperature is lower.
duce high-performance transportation fuels will be necessary. The PP is the lowest temperature at which a liquid will pour or
Fuel performance in diesel engines is directly linked to fluidity flow under prescribed conditions. It is an approximate indication
characteristics in the engine. The highly sophisticated injection of the lowest temperature at which the liquid can still be pumped.
technology relies on quick and complete dispersion within the
combustion chamber. At low ambient temperatures, the cold-
flow properties of typical middle distillate cuts are not adequate.
Several options are typically applied to improve cold-flow
properties in diesel transportation fuels, including kerosine
blending, undercutting, use of additives (mainly at fuel termi-
nals) and catalytic dewaxing. Combined kerosine blending/un-
dercutting with the addition of cold-flow improvers has some
applicability, although it does not work in all cases. As high-val-
ue kerosine is mainly used for jet fuel, blending into lower-value
diesel fuel is only acceptable if there is no alternative outlet.
Seasonal undercutting of middle-distillate fractions will reduce
total diesel yield as higher boiling-point fractions end up in the
low-value fuel oil (FO) pool. FIG. 1. Solidification of diesel fuel in a fuel-filtering device after
The application of versatile cold-flow improvement addi- sudden temperature drop. Photo courtesy of Fordaq IHB.
tives, typically done at product terminals or blending sections,
is very efficient to tailor flow properties like viscosity index (VI) Nonadecane: (C19) 33C (91F)
or pour point (PP). However, the impact on cold-flow filter Hexadecane: (C16) 18C (64F)
plugging point is limited, and the impact on CP may even be Tridecane: (C13) -5C (23F)
negative in some cases.
2,6,10,11-Tetramethylpentadecane: (C19) -100C (-148F)
A selective hydrocracking catalyst has proven to be a robust
approach for catalytic dewaxinga process that can be used to 6-Methyloctadecane: (C19) -4C (25F)
address all aspects of cold-flow performance.a 2-Methyldodecane: (C13) -28C (-18F)
7,8-Dimethyltetradecane: (C16) -86C (122F)
Middle-distillate properties. For diesel fuel, middle distil-
lates have boiling-point curves in the range of 150C (300F) FIG. 2. Simplified molecular structure and melting points of selected
to 400C (750F). In addition to environmental specifications long-chain hydrocarbons typically found in middle-distillate cuts
and diesel fuel.
regarding sulfur, nitrogen and aromatics impurities, combustion
HYDROCARBONPROCESSING JULY 2013
 Refinery of the Future
FIG. 3. Molecular sieving effect for selective cracking of linear
paraffinic molecules in zeolite pores.
The CP is the temperature at which small crystals occur
(turbidity) in defined measurement equipment. The CFPP is the
temperature at which a filter starts to plug in a defined filtration set-
up. If seasonal cold-flow specifications are not met, an unexpected
cold snap can lead to equipment damage, as shown in FIG. 1.
Selective cracking of middle-distillate feedstocks. The
cracking of middle distillate to select paraffinic and isoparaffinic
molecules and their melting points is summarized in FIG. 2.
As the melting point of a particular hydrocarbon molecule in
the middle-distillate fraction is strongly linked to cold-flow
properties, middle distillates with a high content of isoparaffins
have some advantages. Therefore, middle distillates with more
paraffinic hydrocarbons but poor cold-flow properties can be
converted into middle distillates with good cold-flow properties
by increasing the isoparaffin-to-paraffin ratio.
Two types of catalytic conversion are possible: dewaxing
by isomerization, and dewaxing by selective cracking. A
catalyst system can selectively crack paraffinic hydrocarbons
of middle-distillate feedstocks.a The cracking function in this
novel catalyst is performed by a solid-acid ingredient based on
a medium pore-size zeolite that shape-selectively differentiates
between branched isoparaffins and linear normal-paraffins. As
shown in FIG. 3, only unbranched normal paraffins (n-paraffins)
can enter the pores and be converted into smaller molecules via
A) Purge gas
Makeup H2
Feed Gas
Wild naphtha
Guard bed
X HDS bed
Diesel
Catalytic dewaxing bed
Hydrofinishing bed Y Heavies
FIG. 4. Dewaxing by selective cracking with hydrocracking catalyst in a stand-alone unit (a), or within an existing middle-distillate
hydrotreating unit (b).
HYDROCARBONPROCESSING JULY 2013
cracking. The catalyst includes a zeolite with a unique acidity
profile that provides outstanding robustness and flexibility for
use with a variety of feedstocks.a In addition, a second catalytic-
base-metal function allows fast hydrogen transfer for efficient
product release and coke prevention.
Dewaxing service. The catalyst has been commercially
available for nearly 20 years. It can be used as a stand-alone
solution, or within an existing middle-distillate hydrotreater or
ultra-low-sulfur diesel unit, as shown in FIG. 4. Middle distillates
with a wide variety of cut points can be processed. As basic
nitrogen has a particular influence on total catalyst activity, the
placement of a small bed of cobalt (Co)-molybdenum (Mo) or
nickel (Ni)-Mo hydrotreating catalysts in front can be helpful,
particularly for a stand-alone operation.b
Using selective-hydrocracking catalysts within an existing
middle-distillate hydrotreating unit is a very common
practice. This catalyst can be used with nearly all types
of feedstocks, whether straight-run or converted (such
as cracker or visbreaker or coker gasoil) refinery product
streams, as shown in TABLE 1. Its properties are tailored to fit
to all hydrotreating catalysts commercially available. Selective
cracking is an endothermic process; therefore, the placement
of a hydrocracking catalyst bed between two hydrotreating
catalyst beds in a hydrodesulfurization (HDS) reactor allows
optimum heat integration and very favorable product qualities
for cold flow and color. Moreover, commercial experience
confirms the control of dewaxing activity according to
seasonal demand even without quenching capabilities. In some
cases, a two-reactor solution with bypass lines, as represented in
FIG. 5, is the most favorable.
The use of selective hydrocracking catalysts can moderately
reduce diesel production and increase hydrogen consumption,
depending on operational severity and cold-flow improvement
requirements. However, many selective hydrocracking
installations circumvent diesel yield loss by applying feedstock
components with higher final boiling point (higher cut
point). This action allows the conversion of a portion of non-
blendable intermediates into higher-value diesel components to
compensate for reduced diesel production.
An additional feature of the selective-hydrocracking
catalyst system is the reduced gas-make. This is very important
Purge gas
B) H2S
Makeup H2
Feed Gas
Wild naphtha
Amine unit
X
Diesel
HDS bed X
Catalytic dewaxing bed
Hydrofinishing bed Y Heavies
 Refinery of the Future

Purge gas TABLE 1. General specifications of a new dewaxing catalyst in

H2S combination with HDS operation
Makeup H2
Feed Gas Applicable feedstocks LGO, HGO, VGO, VBGO, LCGO,
HCGO, CGO

Wild naphtha Operation pressure, bar (psi) 30150 (4352,000)

Operation temperature, C (F) 280380 (530720)
Amine unit
HDS Diesel
Catalytic LHSV according to cold-flow 0.58
HDS dewaxing improvement service, h1
Hydro-
finishing Tolerance to sulfur, wt% < 2.5
HDS
Heavies Tolerance to basic nitrogen, wt-ppm < 1,000
Regenerability Yes (in-situ and ex-situ)
Presulfiding According to HDS catalyst
FIG. 5. Combined hydrotreating and dewaxing unit for optimal procedure
seasonal diesel service.
Production: Light hydrocarbons, wt% 0.55
Naphtha, wt% 115
for existing hydrotreating units, as the formation of light Diesel, wt% 8099
hydrocarbons has no big impact on recycle gas density.
Therefore, it does not interfere with the recycle-gas compressor LITERATURE CITED
operation. Finally, using a selective dewaxing catalyst as a 1
Koehler, E. O., Catalytic dewaxing with zeolites for improved profitability of
drop-in replacement does not require cost intensive revamp or ULSD production in from zeolites to porous materials, 40th International Zeolite
exchange of recycle compressors. Only minimal modifications Conference.
of product stabilizers may be necessary to handle higher
2
Xu, R., Z. Gao, J. Chen and W. Yan, Studies in surface science and catalysis, Elsevier,
2007, p. 7.
naphtha volumes in rare cases. 3
Weyda, H. and E. Koehler, Proceedings of the 12th Symposium of KFUPM
Research Institute, December 2002.
ACKNOWLEDGMENT
The article is a revised and updated version from an earlier presentation at the DR. RAINER ALBERT RAKOCZY is the global product manager for zeolite-based
American Fuel and Petrochemical Manufacturers (AFPM) Annual Meeting, March fuel upgrading and fuel production catalysts with Clariant. He started with Sd-
1719, 2013, at San Antonio, Texas. Chemie in 2005 and headed the solid-catalyst research department. Dr. Rakoczy
studied chemistry at the University of Stuttgart and worked also in the field of PCB
production (IBM and Hewlett-Packard) and microprocess engineering (FZ Karlsruhe).
NOTES
Dr. Rakoczy has a deep background in the field of zeolites. He is an elected member
a
HYDEX-G is used for selective hydrocracking of long-chain n-paraffins to of the Zeolite Group board of the German ProcessNet Association (DECHEMA).
improve the cold-flow properties of middle distillates. Its most common applica-
tion is for sulfur-containing diesel streams in combination with HDS catalysts in DR. PAIGE MARIE MORSE is the global marketing manager for the catalysts business
an integrated system. It is a registered product of Clariant. of Clariant; she is based in Munich, Germany. Previously, she held technical and
b
HDMax is a hydrotreating catalyst series developed primarily for severe hydrotreat- business development roles at Dow and Shell in the US. Dr. Morse holds a PhD in
ing operation of waxes and lube oil stocks. It is a registered product of Clariant. chemistry from the University of Illinois.

Article copyright 2013 by Gulf Publishing Company. All rights reserved. Printed in U.S.A.
Not to be distributed in electronic or printed form, or posted on a website, without express written permission of copyright holder.
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