2016 (Book) Regeneration of Spent Catalyst and Impregnation of Catalyst by S

CHEMISTRY RESEARCH AND APPLICATIONS
REGENERATION OF SPENT CATALYST

AND IMPREGNATION OF CATALYST
BY SUPERCRITICAL FLUID
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REGENERATION OF SPENT CATALYST

AND IMPREGNATION OF CATALYST
BY SUPERCRITICAL FLUID
FARID GUMEROV
AND
BERNARD LE NEINDRE
EDITORS
New York
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CONTENTS
Preface vii
About the Editors xvii
Chapter 1 Regeneration of Palladium Catalysts G-58E Used in
the Hydrogenation Process of Ethane-Ethylene Fraction
by Supercritical Carbon Dioxide 1
T. R. Bilalov, F. M. Gumerov, F. R. Gabitov,
Kh. E. Kharlampidi, G. I. Fedorov, R. S. Yarullin
and I. A. Yakushev
Chapter 2 Regeneration of Nickel on Kieselguhr Catalyst Used in the Process
of Separation of Acetylene Compounds from Isoprene
by Supercritical СО2 Extraction 23
R. F. Gallyamov, А. А. Sagdeev, F. M. Gumerov
and F. R. Gabitov
Chapter 3 Regeneration of the Active Alumina Catalyst Used in the Methyl
Phenyl Carbinol Dehydration Process by Supercritical
CO2 Extraction 45
A. T. Galimova, A. A. Sagdeev, F. M. Gumerov
and N. N. Sarimov
Chapter 4 Regeneration of LD-265 Palladium Catalyst Used in the
Hydrogenation of Diene Hydrocarbons by Supercritical
CO2 Extraction 77
K. A. Sagdeev, A. A. Sagdeev, F. M. Gumerov, Z. I. Zaripov
and B. Le Neindre
Chapter 5 Regeneration of DN-3531 and Criterion 514 Nickel-Molybdenum
Catalysts Used in Kerosene and Gas Oil Hydrotreating
by Supercritical Carbon Dioxide Extraction 109
A. A. Jaddoa, T. R. Bilalov, F. M. Gumerov, F. R. Gabitov,
Kh. E. Kharlampidi and B. T. Burganov
vi Contents
Chapter 6 Synthesis of the Palladium Catalyst by Supercritical

СO2 Impregnation Method Performed in Static and Dynamic Modes 141
T. R. Bilalov, A. A. Zakharov, B. T. Burganov, F. M. Gumerov,
Kh. E. Kharlampidi and G. I. Fedorov
Conclusion 157
Acknowledgment 159
Index 161
PREFACE
In recent years the chemical and oil industries are undergoing their most serious
challenge technically, economically and environmentally, as new processes are gradually
being introduced in many markets. These industrial changes come from a greater need for
productivity and economic improvement.
Most industrial processes would not be feasible without catalysts, so it is particularly
important to understand all the factors that determine the catalytic properties. Large amounts
of catalysts are used in the petroleum refining and petrochemical industry to upgrade the
different flows of petroleum and residues, and the usual production of gasoline, diesel fuels,
jet fuels, heavy oil hydrocarbons, petrochemicals and plastics. In addition, with the rapid
development and wide application of catalysis technology, more and more sophisticated
catalysts are introduced in refining and petrochemical applications, in order to increase the
catalytic performance. This leads to manage refining and petrochemical units differently.
A catalyst is a material of constant composition (gas, liquid, or solid), that increases the
rate of a chemical reaction by providing an appropriate reaction pathway, with the lowest
activation energy. As the activation energy is lower, more reaction products will be formed in
the same period of time. Heterogeneous catalysis differed from homogeneous catalysis in the
number of phases present during the reaction. The heterogeneous catalysis is a surface
phenomenon, wherein the catalyst phase, solid mostly, differs from that of the reactants.
After periods of operation, the catalysts undergo mechanical, physical and chemical
changes with a consequent more or less rapid loss in activity and often in selectivity. In
chemical processes, the progressive deactivation of solid catalysts is a major economic
concern and the control of their stability, activity and selectivity has become crucial. For these
reasons, there is a strong motivation to understand the mechanisms leading to any loss in
activity and/or selectivity and to find out the efficient preventive measures and regenerative
solutions that open the way to cheaper and cleaner processes.
Most of the catalysts used in the refining or petrochemical applications deactivate more
or less quickly with time. The time scales for the deactivation catalyst vary considerably with
the process, and has profound consequences for process design. The design of fixed bed
catalytic reactors is based on the kinetics of deactivation of the catalyst, so that the catalyst
life is at least six months and typically several years. This decrease in activity can be
compensated by changing some operating parameters. However, at some point, catalyst
replacement is inevitable.
Catalyst deactivation is a complex phenomenon, generally defined as the loss of catalytic
activity and selectivity over time. Catalyst deactivation is attributed to changes in the
viii Farid Gumerov and B. Le Neindre
structure and state of the catalyst, due to the interaction between the catalyst and the
impurities present in the feed stream, wherein the catalyst is used. It is a problem of great and
ongoing concern in the practice of industrial catalytic processes. The costs to industry for
catalyst replacement and process shutdown amount to billions of dollars per year.
The main causes of deactivation of solid catalysts and their mechanisms were reviewed s
by Bartholomew [1]. The causes of deactivation can be grouped into five types [1-4]: (a)
Poisoning by strong chemisorptions of species; (b) Formation of deposits on the catalyst; (c)
Chemical and structural alterations of the catalysts; (d) Mechanical alterations; (e) Leaching
of active species. In commercial processes, catalyst deactivation is often due to several of
these causes with interdependent effects.
The activity of the catalyst gradually declines due, mainly, to the building-up of coke
which plays a crucial role in the operation of the reformer under industrial conditions. There
are numerous reactions and mechanisms of coke formation, depending on the nature of the
catalyst, whether it is a pure metal, or contains additional non-metallic elements to increase
the selectivity [1]. The coke formation is strongly dependent on temperature and feedstocks.
Refinery feedstocks, in general, are extremely complicated chemical mixtures in which each
heteroatom is present in the form of literally hundreds of different compounds.
Much of the coke formation arises due to carbon molecules adsorbed on the surface of
the metal compound to form multiple layers, covering the active sites of the surface of the
heterogeneous catalyst, therefore, decreasing the active surface area of the catalyst and
reducing its yield and selectivity. In certain circumstances when carbon compounds become
trapped in the pores, they can cause unusual stress increase within the pore, which can break
the catalyst [1].
In addition, the metal oxide catalysts contain acidic pore spaces that affect the coke
formation. These acidic pores modify the behavior of carbon atoms in the cyclic and aromatic
chains, which link with carbon radicals, to form high molecular weight compounds that stick
to catalysts and are difficult to remove.
Coke formation is believed to result from cracking and polymerization reactions; perhaps
from the deposition of coke precursors such as anthracene, coronene, ovalene and other
condensed ring aromatic molecules on the catalyst, these polymerizing to form coke. It is
possible to recover a large part of the initial catalytic activity when the deactivation is
reversible (such as coke fouling). During operation, the temperature of the process is
gradually raised to compensate for the activity loss caused by coke deposition. Eventually,
however, economics dictates the necessity of reactivating the catalyst. Consequently, in all
processes of this type the catalyst must necessarily be periodically regenerated by removal of
the coke from the catalyst.
Coke removal by oxidation is a difficult task and requires a careful control of the
temperature. Typically, in the regeneration, the coke is burned from the catalyst at controlled
conditions. In a regeneration of this type, the catalyst is contacted with oxygen at flame front
temperatures ranging about 700 K. to about 850 K., this being generally followed by a
secondary burn with increased oxygen concentrations as coke is depleted from the catalyst.
The reaction is highly exothermic and can result in overheating and sample thermal
reorganization. The final result is the loss of surface area (sintering) and the formation of
refractory compounds. Coke has also been removed from catalysts by contact with hydrogen
at elevated temperature.
Preface ix
Deactivation by poisoning involves chemisorption on the active sites of the competing

poison molecules with reactive molecules. Poisoning occurs when there is a loss of catalytic
activity due to substances that interact strongly and irreversibly with the active sites of the
catalyst. The most common impurities found in the feed streams are sulfur, phosphorus, zinc,
calcium, arsenic, alkali metals, heavy metals, iron, and chlorides present in gaseous form or
as micron size particles. Since these substances accumulate on the surface of catalysts, they
are in competition with other impurities for space on the surface area of catalysts. In addition
to physically blocking adsorption sites, adsorbed poisons may induce changes in the
electronic or geometric structure of the surface [5].
Sintering generally refers to a structural modification of the active surface of the catalyst
due to high temperature and / or pressure. Sintering occurs either due to metal atoms, which
migrate from one crystallite to another, through the surface or in the gas phase, by reducing
the small crystallite size and increasing the larger ones, or by migration of the crystallites
along the surface, followed by collision and coalescence of two crystallites [5-6]. It should be
noted that the sintering rate increases exponentially with temperature and becomes more and
more pronounced above temperatures of 900 K.
Catalyst regeneration involves the processing of spent catalysts in order to make them
reusable. This is done by restoring the chemical properties of spent catalysts and thus
restoring their efficiency through a process called regeneration of catalyst. There are several
reasons for regeneration. Initially, the reasons were economic, while later awareness was
brought about by environmental concerns about disposals. The main advantage of catalyst
regeneration is that it costs less than fresh catalysts.
If a catalyst has been deactivated by the surface deposition of a foreign substance or by
the incorporation of a removable poison, it may be possible to regenerate the catalyst and
restore the catalytic activity. Regeneration of deactivated catalysts is possible for most of
catalytic processes and is widely practiced. The main purpose is to eliminate the temporary
poisons on the catalyst surface and restore the free adsorption sites. If the regeneration is
technically possible, it is the preferred option for the environment and economically to face
the spent catalysts; it facilitates prolonged use of the catalyst, minimizing the use of new raw
materials and reduces the need for definitive recovery of disposal.
Along with the rapid development and wide application of catalysis technology, the
amounts of different spent catalysts are increased from year to year. In addition, catalysts
have thus become more and more sophisticated and one indirect consequence is that they
need more careful procedures for regeneration than in the past.
Depending primarily on the chemical and structural changes in the catalyst during use,
the user is faced with a number of options for dealing with the spent material. Several
methods such as disposal in landfills, recovery of some or all of the components in the
material, use of the material in another process, reuse of the material by regeneration and
rejuvenation and utilization as raw materials to produce other useful products are available for
the users, which deal with the spent catalyst problem. The choice between these options
depends on technical feasibility and economic consideration.
Disposal of a spent catalyst landfill is always the least environmentally preferred option,
and is an option that requires compliance with stringent environmental regulations. Landfill
does not remove or destroy any hazardous materials which, if the risks are not properly
managed, can pose long term health and environmental risk.
x Farid Gumerov and B. Le Neindre
Safe disposal of a spent catalyst is a major environmental problem, as landfill disposal is

no longer generally accepted as the best practice. Environmental laws concerning spent
catalyst disposal have becomes increasingly more severe in recent years. Landfill does not
remove or destroy any hazardous materials which, if the threats are not properly managed,
can pose long term health and environmental risks, and be affected by future regulatory
changes. In many countries, the spent catalysts have been classified as hazardous waste
material and are subject to strict guidelines for disposal. Most major refinery companies have
set up special disposal practices and enable authorized waste collectors and processors to
dispose the catalyst waste.
In the USA, the current regulations of the Resource Conservation and Recovery Act
(RCRA) require landfill to be built with double liners and with leachate collection and
groundwater monitoring facilities. Thus, the landfill option is more expensive today. In
addition, it carries with it a continuous environmental responsibility for the life of the dumb-
site. Treatment prior to filling of the land may be necessary in some cases, which further
increases the cost.
Catalysts that can be regenerated are usually able to be used through several operation
regeneration cycles. It is important to note that in the case of regeneration of spent catalyst,
the product often does not change the ownership, and that its original economic value is fully
recovered and exploitable.
The spent catalysts are generally treated as harmless industrial waste, but their
characteristics are varied in different processes and condition. If the spent catalysts can be
regenerated and activated effectively, they can be reused with higher values and economic
efficiency.
The physical properties of spent catalysts, as well as their composition, are generally
different from those of fresh catalysts. For example, spent hydrotreating catalysts contain
metal sulfides and coke and may have additional contaminants that were not present in the
fresh catalyst.
The catalyst regeneration market is divided into two regeneration technologies: off-site
and on-site. Both regeneration technologies have specific requirements of catalyst
regeneration, such as refinery, chemicals, and petrochemicals which differ in cost and
efficiency. In the off-site (ex-situ) regeneration, the catalyst is discharged from the reactor.
The on-site (in-situ) regeneration does not require removal of the catalyst from a reactor.
Generally, the procedure is to burn off, or oxygenate, the temporary poisons, such as green
oil, in order to resume the activity of the catalyst. Regeneration of the catalyst may be
accomplished, for example, by heating the catalyst in air to a temperature over 573 K up to
about 773 K, to incinerate any organic material, polymers, or char.
The off-site catalyst regeneration has the highest market share and is also the fastest
dynamic market. Off-site regeneration is a fast growing technology chosen by the petroleum
refining and chemical and petrochemical industries because of strict environmental
regulations, cost optimization, and better quality and performance of regenerated catalysts.
The price of the regeneration of the catalyst is lower than that of fresh catalysts which
governs the overall market growth. Prices also depend on the methods used, as on and off-site
regeneration. The market for regenerated catalyst, in terms of value, is estimated to reach
$5 billion by 2019, with a compound annual growth rate (CAGR) of 5.54% between 2014 and
2019. Due to the closure of few refineries in Europe, the regenerated catalyst market will
undergo a slow growth rate. In North America, the catalyst regeneration market is expected to
Preface xi
grow quickly in the next years due to the processing of shale gas. In Asia-Pacific, the catalyst
regeneration market is forecast to grow at the highest CAGR between 2014 and 2019 due to
rise in refinery capacity [7].
Many spent catalysts contain sufficient concentrations of precious metal based
constituents, or other materials, to be economically worth recovering; and the recovery of the
precious metals from spent catalysts, by metallurgy processes or direct reuse as the
construction materials, has been well established for many years. The cost of commercial
cobalt, nickel, and molybdenum based catalysts has increased by a factor of four over the last
five years. This has produced a strong economic incentive to regenerate used LC-Fining
catalysts. The recovery of metals not only reduces the amount of wastes for disposal but also
preserves natural resources, then offers an environmentally reliable alternative to landfill
disposal.
Fluctuations in the market prices of the recovered metals and their purity significantly
influence the economics of the metal recovery process, making it less attractive for spent
catalysts that contain low level of metals. However, in recent years, the emphasis has been
placed on the development of processes for recycling spent catalysts that contain high
concentrations of precious metals [8-11].
Many variant of the same type of regeneration process are found in the industry, and the
operating conditions can be quite diverse, depending on the type of catalyst used and the
feedstock processed.
The spent catalysts can be regenerated or reactivated by different physical, chemical and
thermal methods. The advantages in terms of energy savings or environment, associated with
these recycling activities are also very important. It has been estimated that the recycling of
various metal scraps consumes about 33% less energy, and generates 60% less harmful
wastes than the production of fresh catalysts from ore.
In the 1970s, most refiners regenerated their catalysts in-situ, in fixed-bed reactors, as it
was considered that in-situ regeneration was more practical and attractive. As a matter of fact,
the ex-site regeneration delays the continuous operation of industrial processes, as the
catalysis reactors and processes must be stopped for the dismantling of deactivated catalysts
and transport them to the regeneration plant. However, temperature gradients and hot spots
can take place in in-situ regeneration, resulting in sintering of the catalyst and the loss of
activity. Another problem is that catalyst fines remain in the catalyst bed, which can cause
fouling of the reactor and pressure drop when the reactor is restarted.
In-situ regeneration and sulfiding of catalysts in the refinery increase the emissions of
harmful gases from refinery site, like the production of large excess of hydrogen sulfide.
Oxidative regeneration of catalyst is carried out by heating or injection of hot steam,
hydrogen, oxygen, and various oxidizing agents, reducing agents, or organic solvents, in the
catalysis reactor, for coke burning, thus generating CO, CO2, NOx and SOx, which
accumulate in the gas system of the reactor. Each of these gases must be treated in
downstream process units, to reduce pollution from the refinery.
In addition, there are few studies investigating the regeneration efficiency of different
methods and catalysts, and the effects of various operation conditions in the in-situ
regeneration of the deactivated catalysts.
Today, the major refining companies are largely practicing catalyst reuse, and have
abandoned in situ regeneration for different reasons, one being that it took too much
downtime without production, and are encouraging actions which minimize shut down time.
xii Farid Gumerov and B. Le Neindre
Ex-situ regeneration is a booming technology selected by oil refining and chemical and
petrochemical industries, because of strict environmental regulations, cost optimization, and
better quality and performance of the regenerated catalysts. Today, 90 to 95% of the catalyst
regenerated in the U.S. and in Europe is regenerated ex situ. The off-site catalyst regeneration
has the highest market share and is also the fastest growing market.
Ex-situ regeneration has several advantages over in-situ regeneration. Ex-situ
regeneration of catalysts results in better recovery of activity due to close control of the
regeneration temperature, a better evaluation of the catalyst for reuse, through a variety of
tests for characterization and quality control, and a chance to remove fines and chips that
contribute to pressure drop problems. The safety of the environment and the reduction of
delays of shutdown and start up of units, are the additional benefits of ex-situ regeneration,
because the in-situ regeneration is longer and more difficult to control. In-situ regeneration
recovered only 50 to 60% of the catalyst activity, while ex-situ regeneration retrieves
75 to 95%.
The chemical treatment is one of the popular methods of regeneration of spent catalysts.
Various acidic or alkaline solutions have been used to regenerate the spent catalysts, such as
oxalic acid, HCl, HNO3, NaOH, H2SO4, VOSO4, (NH4)2WO4, acetic acid, and citric acid. The
main function of these solutions in catalyst regeneration is to remove the blocked carbons or
poisoned residues from the spent catalysts. The effects of various chemical reagents,
concentrations, and operating conditions on catalyst regeneration vary with different spent
catalysts (active metals and compositions) [7].
Oil refining and petrochemical plants are currently undergoing serious challenges from a
technical and economical point of view, as well as from an environmental point of view.
This document will provide a brief overview of the management practices and
regeneration of spent catalysts, with the focus on the technologies, issues and opportunities
related to the preservation of the environment.
The spent catalysts which were regenerate in this study, are commercial catalysts
unloaded from different type of industrial units, developed by Nizhnekamsk Chemical
Industries, Nizhnekamsk, Russia. Most of the data presented here were obtained in the
laboratories of Kazan National Research Technological University, in Russia.
The analysis of deactivated compounds was carried out for industrial catalysts such as: a)
G-58E grade palladium for the selective hydrogenation of ethane-ethylene; b) nickel-on-
kieselguhr for the separation of acetylene compounds from isoprene; c) “active aluminum
oxide” for methyl phenyl carbinol dehydration process; d) LD-265 grade palladium for the
hydrogenation process of hydrocarbon; e) Dn-3531 and Criterion 514, nickel-molybdenum
grades for hydrotreatment of kerosene and gas oil. In most refineries, the majority of spent
catalyst waste comes from the residue of hydrotreating and hydroprocessing units. This is
because the catalysts used in these processes deactivate rapidly by coke and metal (Mo and
Ni) deposits, and have a short life.
Another important subject present in this volume is the measurement of solubility of
compounds extracted from deactivated catalysts.
The solubility of deactivated catalyst compounds was carried out in pure supercritical
carbon dioxide and supercritical carbon dioxide modified with polar co-solvents. CO2 is a
non-polar solvent that can be used in liquid or supercritical states. Liquid CO2 is significantly
less polar solvent than supercritical CO2, and is limited to the extraction of small non-polar
molecules. The solubility was described using the Peng-Robinson equation state.
Preface xiii
At this time, for industrial applications, sub and supercritical fluids can be considered as
the most promising innovative technologies. Supercritical fluids combined the advantages of
both gaseous and liquid properties. They greatly intensify heat and mass transfer processes as
the thermal conductivity and the specific heat at constant pressure, diverge near the critical
point. If we consider the kinematic viscosity (υ = η/ρ), supercritical fluids have values which
are one to two orders of magnitude lower than the classical liquid organic solvents. As the
kinematic viscosity is presented in the denominators of Grashof and Reynolds numbers, its
produces a significant increase of the degrees of freedom and forced convection in SCF
media. The diffusivity (binary diffusion, self-diffusion) of supercritical fluid media is one to
two orders of magnitude higher than the one of liquid organic solvents. Supercritical fluid
media have no phase boundary, no surface tension, and therefore no capillary effect; then they
show high degree of penetration into the porous structures. Moreover, the residues are easy to
recover and the extractant can be recycled. With their original properties we believe than
supercritical fluids provide significant opportunities for the synthesis and regeneration of
heterogeneous catalysts. The success of this approach has been confirmed not only by
numerous studies but also by many industrial achievements.
The key parameter to be analyzed in this innovative process is the solubility of
deactivated compounds of catalyst in SCF media, related to their chemical composition. The
three main factors that govern the solubility of a substance in a given solvent are the nature of
the solute and solvent, their states of aggregation and the thermodynamic conditions. Two
opposite trends control the nature of ongoing modifications of the solubility of the substance
in a supercritical fluid solvent. On the one hand, the elevation of the temperature increases the
vapor pressure of the solute and thereby its concentration in the solvent phase increases.
Therefore, there is also an increase in solubility. On the other hand, an increase in temperature
(at P = constant) produces a decrease of the density of the supercritical fluid and a reduction
of its dissolving capacity.
The solubility of substances in supercritical fluid was the subject of intense researches
over the last 2-3 decades [12-16]. They included the development of new experimental
methods and techniques to study this thermodynamic property [17].
The solubility is a property of great practical importance in supercritical fluid media.
However the implementation of new technologies based on SFC in the industry has been very
slow. One reason for this is probably due to the lack of researches on phase equilibrium
characteristics, especially of multi-component systems in supercritical fluid; the other is
related to the absence of significant developments of modeling steps, simulation and
optimization of processes and technology in general.
Specific heat measurements of some compounds have also been reported, they are used to
determine the amount of heat, which may be necessary for the system during the regeneration
process, when it is carried out in an industrial plant. This information is necessary for the
equipment design to the industrial scale.
However, we must acknowledged that the supercritical carbon dioxide extraction process
and impregnation processes by supercritical carbon dioxide, which are already in operation on
a commercial scale, met the industrial requirements for a perfect regeneration and synthesis of
heterogeneous catalysts.
This book brings together highlights of a theme which is growing in interest: the creation
of a sustainable society using catalysis as the main tool. Catalysts play key roles in the
production of clean fuels, the conversion of waste and green raw materials into energy, clean
xiv Farid Gumerov and B. Le Neindre
combustion engines including control of NOx and soot production and reduction of
greenhouse gases, production of clean water and of polymers, as well as reduction from
polymers to monomers. Catalysts are also of major importance in the developing H2 and
syngas production technology, aimed at producing clean fuels for the coming decades, then.
catalysts should be recycled to preserve the resources and the environment.
This book is an overview of processes and operations involved in the regeneration of
catalysts by pure supercritical fluids and supercritical fluids associated with co-solvents. The
objective here is to provide the basic information to regenerate spend catalysts by new
processes that respect the environment.
This book gathered a series of studies describing new methods for the regeneration of
heterogeneous catalysts for important industrial chemical processes. In this book we have
proposed new extraction techniques using supercritical fluid extraction (SFC), which seems to
be one of the most promising as a green reaction medium. The feasibility of using
supercritical fluid СО2 extraction process was investigated in particular for spent catalysts
regeneration. The low regeneration temperature of supercritical carbon dioxide eliminates the
risk of thermal deterioration of the catalyst, namely the collapse of the pores, prevents the
reduction of the surface area and the sintering, and allows regeneration of catalysts to their
maximum possible activity.
The results of the implementation of the supercritical fluid СО2 extraction process as
regards industrial deactivated catalysts samples are provided. A comparison of the
characteristics of the regenerated catalyst samples by the traditional approach and the
SC-CO2 extraction process is carried out. The possibility of using a supercritical fluid CO2
impregnation technique in the synthesis of a palladium catalyst is studied. The synthesis of
organometallic complexes of palladium chloride-basis is described. The conditions of fluid
dynamic supercritical CO2 impregnation process are implemented. The results of the study of
the solubility thereof in the supercritical carbon dioxide are supplied. A comparison of the
characteristics of the palladium catalyst samples synthesized by the approach of the
impregnation process and conventional SC-CO2 is reported.
We hope this book will serve as a useful tool for both scientists looking in the direction
of supercritical fluid technology, as well as industrial enterprises and research institutions in
the context of solving the problem of increasing the efficiency of existing equipment and
technology.
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Preface xv
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[10] Argyle M. D., Bartholomew C. H. Heterogeneous Catalyst Deactivation and
Regeneration: A Review. Catalysts 2015, 5: 145-269.
[11] McMahon, B. Catalyst Regeneration: The Business Case. Power 2006, 150: 36-39.
[12] Gumerov F. М., Sabirzyanov А.N., Gumerova G.I. Sub- and Supercritical Fluids in
Polymer Processing. Pub. “FEN.” Kazan. 2000, 328 p; 2nd Edition. 2007: p. 336.
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Boca Raton, Fla: CRC Press. 2007: p. 205.
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Raton. 2007: p. 909.
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print.” 2013: p. 903.
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ABOUT THE EDITORS
Farid M. Gumerov – Professor, Federal State Budgetary Educational Institution of

Higher Professional Education “Kazan National Research Technological University,” Kazan,
Russia. Email: gum@kstu.ru.
Bernard Le Neindre – Professor, Université Paris 13, Sorbonne Paris Cité, Laboratoire
des Sciences des Procédés et des Matériaux, CNRS, (UPR 3407), F - 93430, Villetaneuse,
France. Email: bernard.leneindre@lspm.cnrs.fr.
In: Regeneration of Spent Catalyst ISBN: 978-1-63484-309-6
Editors: Farid Gumerov and Bernard Le Neindre © 2016 Nova Science Publishers, Inc.
Chapter 1
REGENERATION OF PALLADIUM CATALYSTS

G-58E USED IN THE HYDROGENATION PROCESS OF
ETHANE-ETHYLENE FRACTION BY SUPERCRITICAL
CARBON DIOXIDE
T. R. Bilalov1, F. M. Gumerov1,*, F. R. Gabitov1,

Kh. E. Kharlampidi1, G. I. Fedorov1, R. S. Yarullin2
and I. A. Yakushev2
1
Federal State Budgetary Educational Institution of Higher Professional Education,
Kazan National Research Technological University, Kazan, Russia
2
Tatneftekhiminvest-kholding, PLP Kazan, Russia
ABSTRACT
The nature of deactivating deposits forming on the palladium catalysts G-58E used
in the hydrogenation process of ethane-ethylene fraction is analyzed. Solubility of
deposits like anthracene, was measured in supercritical carbon dioxide at temperatures
313 and 323 K and pressures from 10 to 35 MPa. The regeneration of deactivated
catalysts was performed in supercritical carbon dioxide at various process conditions,
within the temperature range from 313 to 423 K and pressures 20 and 40 MPa. A
comparison of specific surface areas and activities of freshly prepared and regenerated
catalysts with supercritical carbon dioxide samples showed that the proposed method was
very competitive compared with the traditional regeneration techniques. In addition, the
solubility of benzonitrile, styrene and cyclohexene complexes of palladium chloride in
supercritical carbon dioxide were measured in the temperature range from 308 to 323 K
and pressures from 10 to 32,5 MPa. Results were described with the Peng-Robinson
equation of state.
*
Corresponding author: F. M. Gumerov. E-mail: gum@kstu.ru.
2 T. R. Bilalov, F. M. Gumerov, F. R. Gabitov et al.
Keywords: catalyst regeneration, catalyst activity, supercritical carbon dioxide, solubility,

benzonitrile complex of palladium chloride, styrene complex of palladium chloride,
cyclohexene complex of palladium chloride, Peng-Robinson equation of state
1. INTRODUCTION
The synthesis and regeneration of catalysts used in industry should be optimized to
decrease energy costs and harmful impact on the environment. In the 1970s, manufacturers
began to reconsider the implementation of traditional processes by developing new
environmentally friendly technologies that could lead to energy savings. Several proposals
have been made that these technologies could be based on the use of sub- and supercritical
fluid media. As regards the production and regeneration of catalysts, these supercritical fluids
have a good prospect as solvent and extracting agent for the separation, purification,
synthesis, deposition of active components and the regeneration of deactivated catalysts. In
particular, supercritical fluids were used in catalysis for:
 the preparation of high-porosity materials which are potential catalyst carriers;

 the impregnation of porous carriers with active components, including active metal
complexes with organic ligands and organometallic compounds, followed by their
decomposition and formation of reduced metals or their oxides in the porous
structure;
 the regeneration of catalysts;
 the utilization of spent catalysts;
 the performance of catalytic reactions in supercritical fluid media;
 the replacement of catalytic reactions with noncatalytic ones [1].
Scientific basis of the method extraction by supercritical fluid, for the regeneration of
adsorbents and catalysts was developed fairly long ago. There are few data [1], on industrial
implementation of this method applied to distinct types of catalytic systems. At the same
time, it is clear that the diversity of catalytic systems used in the process industry and their
performance does not allow a universal technology for regeneration to be created. This
implies the need for special studies in almost every case. It is also a reasoned opinion that the
approach in question is reasonable to apply to certain groups, namely, expensive catalysts,
such as, for instance, palladium catalysts.
The use of catalysts in large-tonnage industrial processes is always associated with the
problem of a decrease in their activity. Sometimes, this is related to the formation of deposits
of various kinds in pores and/or on the active surface. Then the need for regeneration arises.
Regeneration can be performed by various methods. The most widely used procedure, which
is of burning deposits out, has several short-comings. Primarily, there is a high probability of
enlargement of active component particles (sintering), and as a result, the irreversible loss of
activity due to the high temperature and uncontrolled burning out of carbonaceous and heavy
organic deposits.
Another method for regeneration is treatment with steam. This is a power consuming
process. Its use can also cause irreversible loss of activity as a result of the rearrangement of
Regeneration of Palladium Catalysts G-58E … 3
the crystal structure of carriers and/or active components during hydrothermal treatment (at
720-830 K).
According to some estimates [1], the use of supercritical fluid extraction for the
regeneration of catalysts doubles energy saving and increases the number of possible
regeneration cycles. The unique properties of supercritical media as solvents also allow
problems with deposition of active catalyst components to be effectively resolved.
The thermodynamic characteristics of the preparation and regeneration of catalysts
mainly include information about the solubility in supercritical fluid solvents of precursors
and deposits of catalyst active component deactivating catalysts.
The aim of this study was to obtain solubility data. The object of study was a palladium
catalyst deposited on alumina. This catalyst is used to remove the acetylene impurities (by
their hydrogenation) from an ethane-ethylene fraction (EEF).
2. HYDROGENATION PROCESS OF ETHANE-ETHYLENE FRACTION;

CHARACTERISTICS OF SPENT CATALYST AND DESCRIPTION OF
ITS TRADITIONAL WAY OF REGENERATION
In the manufacturing of polymer grade ethylene, the removal of acetylene from the
hydrocarbon mixtures obtained in cracking plants is an important step. The ethane-ethylene
cut coming from steam cracking contains approximately 1 wt. % of acetylene. A content of
acetylene in ethylene for petrochemical synthesis should be lower than 0.0001% wt.,
otherwise the quality of ethylene production decreases and the conditions of polymerization
process become worse.
A widely used method to remove acetylene in the ethylene stream is the catalytic
hydrogenation, aiming at reducing its concentration with a minimum loss of ethylene to
ethane. The process must be highly selective since the acetylene content has to be reduced to
less than 5 ppm. For the selective hydrogenation of acetylene in ethylene, low surface area
alumina supports are mostly used.
G-58E catalyst is a palladium catalyst deposited on alumina and is used to remove
acetylene impurities (by their hydrogenation) from a fraction of ethane and ethylene (EEF).
The composition of the catalyst is the following: Pd (0.03 wt. %), Ag (0.20 wt. %), the
support is made of spherical beads of Al2O3 with a diameter of 2.5 to 3.0 mm.
Two reactions competed simultaneously inside hydrogenation reactors [2]:
1. Target hydrogenation reaction of acetylene to ethylene
C2H2 + H2 → C2H4 H298K = - 172 MJ/kmol.
2. Undesirable effect of hydrogenation of ethylene to ethane
C2H4 + H2 → C2H6 H298K = - 137 MJ/kmol.
The catalyst is selected in order to orient in priority the reactions towards the target one
and minimized the second reaction [3].
Besides these two reactions, a direct hydrogenation of acetylene to high molecular weight
saturated and unsaturated hydrocarbons occurs, which is one of the most serious problems in
the acetylene hydrogenation reaction system, because it can produce a catalyst deactivation.
This complex mixture of oligomers and polymers generated in the reactor is commonly
named “green oil.” Green oil polymer is formed by side reactions of the hydrogenation
reaction itself, and it cannot be totally avoided. The polymer formation begins by
dimerization of acetylene with hydrogen to butadiene, followed by oligomerization with
successive addition of acetylene molecules to a base chain molecule adsorbed to the Pd
surface.
The low molecular weight fraction of the green oil, which consisted mostly of C4 ~ C6
olefins, like butene and isobutene, vaporizes into the gas stream. Part of the heavier fraction,
which deposits in the pores of the catalyst, is composed of long aliphatic chains, with a mean
composition CnH(1.8-1.9)n where n varying from 14 to 17, n = 14 ~ 17. The rest of the heavier
fraction is carried away with the gas as fine droplets. In the absence of acetylene no oligomers
are formed. In order to enhance the selectivity of the catalyst and to reduce or prevent a net
loss of ethane, small amounts of carbon monoxide are added to the feed gas.
The H2/C2H2 ratio is the main parameter that has an effect on oligomerization; the
elevation in the temperature of the reaction also contributes to the oligomer formation, as the
age of the catalyst, CO content, etc.
In petrochemical plants this hydrogenation reaction is carried out in a temperature range
from 313 K to 373 K, and at pressure of 1.9 MPa. The volumetric flow rate of the feed stream
of ethane-ethylene fraction is 5.609 m3/h, in a flow reactor with a catalyst load in three layers,
and an intermediate cooling of the ethane-ethylene fraction between the first and the second
layers.
Complete catalyst loading volumes are: layer (1) ~ 12 m3, layer (2) ~ 12 m3, layer (3)
~ 9 m3. This reaction is accompanied by several uncontrolled engineering problems, in
particular the phenomenon of thermal runaway, which is known to occur rather often in
industrial practice.
The accumulation of oligomers and polymers on the surface of the catalyst will reduce
the selectivity of ethylene, due to decreasing effective diffusivities.
The catalyst deactivates over time, and when the activity of the catalyst declines below an
acceptable level, the catalyst has to be regenerated in order to be used again [4]. Regeneration
can be achieved by various methods. The most widely applied procedure is a high
temperature oxygenation stage to burn the deactivating carbonaceous residues from the
catalyst, followed by a hydrogen reduction stage to reactivate the catalyst. Such treatment
which is normally performed under a flow of air or dilute oxygen depends of the
characteristics of the deposits and the thermal stability of the crystal structure; however this
method has several disadvantages. Mainly, there is a high probability of the growth of active
components particles (sintering), and therefore, the irreversible loss of activity due to the high
temperature and uncontrolled burning or heavy organic carbonaceous deposits.
Another method of regeneration is the treatment with steam [5]. It is a power consuming
process. Its use can also cause an irreversible loss of activity due to the rearrangement of the
crystalline structure of carriers and/or active components during the hydrothermal treatment
(723-833K).
According to some estimates [6], the supercritical fluid extraction for the regeneration of
catalysts brings to both energy savings and an increase of the number of possible regeneration
cycles [7, 8].
The application of supercritical fluid media can eliminate a number of weaknesses of
traditional methods. Thus, low viscosity fluids allow them to easily penetrate into the deep
pores without the traditional problems associated with the capillary effect. The variation of
their solubility with the pressure leads to a consistent separation from the various components
of the solution through a gradual release of the pressure.
However, a major drawback of supercritical fluid technology is a lack of information of
solubility in supercritical fluids of components used in the processes. Therefore, the
thermodynamic characteristics of the preparation and regeneration of catalysts must be
known, that includes mainly information on the solubility of the deposits that deactivated
catalyst and the active components of the catalyst precursor in supercritical fluid solvents.
Then, one of the objectives of this work was to make accurate measurements of the solubility
of various compounds in supercritical carbon dioxide. This first study was focused
predominantly on the behavior of palladium catalyst deposited on alumina.
3. MATERIALS, EQUIPMENTS, APPLIED RESEARCH METHODS

Solubility measurements were carried out in an apparatus shown in Figure 1, under
dynamic conditions.
The sample was placed into cell (8). The cell was weighed and installed in the air
thermostat (7). Liquid pump (4) was used to supply gas (CO2) at a constant flow rate into a
high pressure vessel (1), through a moisture eliminator filter (2), filled with silica gel. Before
entering the pump, the gas is cooled by a refrigerant, in the refrigerator (3) at a temperature of
378 K. This caused its liquefaction.
The pressure in the system was measured using a standard pressure gauge (9), resulting in
total operating performance installed of ± 0.15%, which is maintained constant to within
± 0.025 MPa, with a pressure controller (10). Before acquiring the temperature and the
pressure set for the experiment, the carbon dioxide is passed through a pipe bypassing the
cell.
When the required parameters are reached, the flow was switched to the line with the cell
containing the test substance. The duration of SC-CO2 pumping through the cell was
determined by the solubility of the substance and the need to ensure the acceptable weighing
accuracy when the dissolved substance was removed. After the prescribed time has elapsed,
the pressure in the system was reduced to atmospheric pressure, and the cell was removed
from the thermostat and weighed again. The difference in weight indicates the amount of
dissolved substance. The flow rate of SC-CO2 at which solubility measurements in dynamic
conditions could be considered as correct has been selected on the basis of a preliminary
study of the dependence of the concentration of the solute on flow rate [9]. The flow rate
corresponding to the highest (equilibrium) concentration of the substance was used.
The regeneration of the spent catalyst was performed on an apparatus shown in Figure 2,
under dynamic conditions.
Analyzed catalyst is set into the cell which is placed in the extractor (1), where upon the
latter is immersed in the thermostat (9). Supercritical carbon dioxide is brought to a
predetermined pressure, generated by the thermo-compressor (3). Simultaneously, the
thermostat with the extractor inside is heated to a predetermined temperature. When the
appropriate parameters of the experiment are obtained, the valve (5) is opened and the fluid
containing the dissolved contaminant goes into the expansion device. The appropriate
pressure is obtained by the manipulation of the valves (5) and (8). Expansion device allows
controlling the supercritical fluid flow rate. The amount of carbon dioxide used in the
experiment, is determined by weighing.
A schematic diagram of the apparatus for preliminary reduction of palladium catalysts
with hydrogen and studies of the activity of the samples after impregnation and regeneration
is shown in Figure 3.
For preliminary reduction, a sample consisting of a complex deposit of volume 0.5 cm3,
of particle size of 0.2 to 0.5 mm, was loaded into the middle of reactor (4); the temperature of
the reactor was controlled by a thermocouple junction (6) connected to the heat regulator (7).
For further heating the gas stream entering the reactor, a layer of inert material (crushed
quartz glass or porcelain with a particle size 0.2 to 0.5 mm) was set up above the catalyst bed.
Hydrogen flow rate was controlled by valves (1) and (3) and measured by a film
flowmeter at the outlet. Then, the temperature in the reactor was lowered to a value selected
for hydrogenation of acetylene, the hydrogen flow was stopped, and a mixture of ethane and
ethylene was introduced. Its composition was (in vol. %): CH4- traces; C2H2- (0.3 vol. %);
C2H4- (80.9 vol. %); C2H6- (16.3 vol. %); and H2- (2.0 vol. %).
Figure 1. Diagram of the experimental apparatus for dynamic solubility measurements; (1) - cylinder
filled with CO2; (2) - moisture filter; (3) - refrigerator; (4), (6) - pumps; (5) - high pressure vessel filled
with solvent; (7) - air thermostat; (8) - extractor; (9) - manometer; (10) - pressure controller; (11) -
vessel filled with water.
Figure 2. Diagram of the experimental apparatus for catalyst regeneration: (1) - СО2 bulb, (2) - filter,
(3) - refrigerator, (4) - thermo-compressor cell, (5) - extraction cell, (6) - extract collection vessel,
(7) - weighing platform, (8) - thermo-compressor heater, (9) - valve, (10) - temperature and pressure
controller and indicator.
Figure 3. Diagram of the experimental set up for catalyst activity measurements: (1) - needle valve;
(2) - MTI pressure gauge; (3) - fine control valve; (4) - reactor; (5) - electrical furnace; (6) -
thermocouple; (7) - heat controller; (8) - three-way cock valve.
The initial ethane - ethylene mixture and the gaseous mixture leaving the reactor were
analyzed on a KHROM-4 chromatograph, with a flame ionization detector. Components of
the mixture were separated at 344 K, and a carrier gas (nitrogen) was injected at a flow rate of
25 cm3/min, in a column of 3 m long and 3 mm inside diameter, packed with -Al2O3 +
NaHCO3 (6 wt. %). The frequency of sampling gas mixture from the reactor was one per
hour. When the complete absence of acetylene was observed at certain reactor temperature
and ethane - ethylene mixture flow rate, the volume flow rate was increased to a value at
which the content of acetylene in the output of the reactor was 1 to 2 ppm. Only this volume
rate of ethane-ethylene mixture was used as a characteristic of the activity of a given catalyst
at the selected temperature.
The reduction continued for 2 to 3 hours at about 523 K, in a flow of hydrogen.
The activity of catalysts was calculated from the conversion ratio of acetylene by the
relation:
X = (Cin - Cout)/Cin,
where X is the conversion ratio and Cin and Cout are the acetylene concentrations at the input
and output of the reactor, respectively.
Studies of catalysts regenerated by the thermal analysis method were performed on a
Q-1500 D (MOM) derivatograph in the temperature range from 293 to 1273 K, in corundum
crucibles, in air; sample weights were 200 mg. The error of temperature measurement was
± 5 K, and the relative error on weight measurements at a preset sensitivity of 0.2 mg
was ± 0.5%. This instrument could be used to simultaneously measure weight changes of
samples (TG), the rate of sample weight changes (thermogravimetry and DTG), and the
effects of heat (differential thermal analysis, DTA).
4. SOLUBILITY COMPOUNDS OF DEACTIVATION OF CATALYST

IN PURE AND MODIFIED SUPERCRITICAL CARBON DIOXIDE
WITH POLAR ADDITIVES
It is well known that coke is the primary contaminant of the spent catalyst. It comprises
the following classes of substances: aliphatic hydrocarbons, diene hydrocarbons, aromatic and
polyaromatic compounds, naphthalene and linear oligomers [10]. One component of the coke
formed on the catalyst surface is anthracene [11]. Its solubility was measured in the apparatus
shown in Figure 1, at temperatures T = 313.15 K and T = 323.15 K, in the pressure range of
11.0 to 35.0 MPa. The results of the measurements, as well as literature data [12], are shown
in Figure 4; the mass flow rate of supercritical carbon dioxide was 0.5 gram per minute. The
influence of co-solvents on the solubility of anthracene was also studied. The co-solvents
used were acetone and dimethyl sulfoxide, whose concentrations were varied from zero
to 7.5 wt. %. The results of measurements at 323.15 K and 24.5 MPa are shown in Figure 5.
When the concentration of co-solvent increases, the solubility of anthracene reaches a
maximum, corresponding to the optimum content of the co-solvent (about 5 wt. %) during the
regeneration.
5. REGENERATION OF PALLADIUM CATALYSTS G-58E

USED IN HYDROGENATION PROCESS OF ETHANE-ETHYLENE
FRACTION BY MEANS OF SUPERCRITICAL CARBON DIOXIDE
The regeneration of a G-58E catalyst was performed at 313 to 323 K, and pressures from
10 to 40 MPa. In all the experiments, acetone was used as a co-solvent; its concentration in
SC-CO2 was 3 wt. %.
The kinetics of regeneration of the catalyst is shown in Figure 6. Based on data on the
specific surface areas of catalyst samples (Table 1), the most complete regeneration was
achieved at 323 K and 40 MPa (Sample 3), which was in agreement with the data on the
kinetics of regeneration. The surface area of the regenerated sample was smaller than that of
the freshly prepared catalyst; it was only 78% of the maximum value. One reason for the
incomplete regeneration could be the presence of substances poorly soluble in SC-CO2
modified with acetone in deposits. In addition, the acetone concentration was below the
optimum value for the maximum extraction capacity of solution of SC-CO2 modified, when
compared to the modeling of deactivation of deposits (anthracene).
The method of measurement of specific surface area was described by Nelsen et al. [13].
Figure 4. Solubility of anthracene in SC-CO2: (1) [11] and (2) this work.
Figure 5. Solubility of anthracene in modified supercritical carbon dioxide: (1) - with acetone and (2) -
with dimethyl sulfoxide.
Figure 6. Relative G-58E catalyst weight variations (dm/M) during the regeneration by means of SC-
CO2 at: (1) - 20 MPa and 313 K; (2) - 20 MPa and 423 K; (3) - 40 MPa and 423 K; and (4) - 20 MPa
and 353 K.
Table 1. Surface areas of G-58E catalyst samples
Peak Peak Peak Volume of Specific

Regeneration
No. Weight, g Scale height, width, area, nitrogen, surface area,
parameters
mm mm mm2 cm3 m2/g
Freshly
0 prepared 0.083 64 144 1.3 11980.8 2.731 160.573
catalyst
P = 20 MPa,
1 0.110 32 210 1.1 7392 1.074 47.632
T = 413 K
P = 20 MPa,
2 0.105 32 231 1.1 8131.2 1.245 57.879
T = 423 K
P = 40 MPa,
3 0.098 64 135 1.3 11232 2.521 125.550
T = 423 K
P = 20 MPa,
4 0.105 16 192 1.2 3686.4 0.827 38.459
T = 353 K
6. COMPARISON OF CHARACTERISTICS OF REGENERATED

CATALYST SAMPLES USING THE TRADITIONAL APPROACH
AND THE SC-CO2 EXTRACTION PROCESS
The activity of the catalyst regenerated with the use of SC-CO2 was studied for the
example of the most completely regenerated sample (Table 1, sample 3). For comparison, we
also measured the activities of the freshly prepared and used catalysts and a catalyst
regenerated following the traditional technology. Regeneration according to the traditional
technology was performed by oxidative annealing of the spent sample in air at 833 K. The
results are listed in Table 2.
These data show that the regeneration of the catalysts by the method proposed in this
work restores the catalyst activity. Optionally, the selection of a more efficient and optimal
polar co-solvent concentration (e.g., dimethyl sulfoxide at a concentration of 5 wt. %, as
shown in Figure 5, where the maximum solubility of dimethyl sulfoxide is observed) in the
absence of an irreversible poisoning can ensure the regeneration of the catalyst and make its
full activity close to that of a freshly prepared sample in the same conditions.
Overall, the method of extraction with supercritical fluid is less energy consuming, and
the experimental conditions are more protective of the catalysts.
Two catalyst samples regenerated by the traditional and SC-CO2 methods were studied
by complex thermal analysis. The results are shown in Figures 7 and 8. The form of the
thermo-analytical curves shows that the samples are almost identical. Both samples lose
weight from 298 K to 473 K and from 473 K to 873 K (curves 1 and 2). The first weight loss,
at low temperature corresponds to the elimination of weakly bound water (peaks A and C).
The second weight loss is probably related to the combustion of coke (peak B). This is
corroborated by the presence of an exothermic effect (curve 3, peak E), which is evidence of
an oxidation process. Coke burning out is recorded for both samples at close temperatures.
Table 2. Activities of G-58E catalyst samples
Rate of hydrogenation of acetylene (%) as a function of

Catalyst sample temperature (K)
333 343 353 373 393 423
Freshly prepared catalyst 31.7 69.3 100.0* - - -
Used catalyst - - - 17.1 23.5 30.2
Catalyst regenerated by SC-
- - - 41.1 53.1 100.0*
CO2
Catalyst regenerated by the
- 20.5 33.2 100.0*
traditional method
*
Acetylene hydrogenation depth in an ethane-ethylene mixture was considered to be 100%, when the
content of acetylene in a purified mixture did not exceed 0.01 vol. %.
The characteristics which are different between the two samples are the followings:
The sample shown in Figure 7 undergoes a greater weight loss corresponding to the
removal of adsorbed water compared with the sample shown in Figure 8 (3.3 and 1.8 wt. %,
respectively). An exothermic effect with a maximum at 443 K (peak D) is observed in Figure
7, between 393 K and 505 K; this peak corresponds to the combustion of organic
components, it is lower in Figure 8.
With the presence of coke in the two samples, it is obvious that both the traditional
procedures and SC-CO2 provide incomplete regeneration of the samples studied. Overall, the
data presented above are evidence of opportunities of the two regeneration methods.
However, the SC fluid method is better in terms of energy saving and the possibility of a
larger number of regeneration cycles; which increase the life of the catalysts.
Figure 7. Thermal analysis of the catalyst regenerated by the traditional method: (1) - sample weight
changes, (2) - rate of sample weight changes, (3) - DTA measurement.
Figure 8. Thermal analysis of the catalyst regenerated in SC-CO2: (1) - sample weight changes, (2) -
rate of sample weight changes, and (3) - DTA measurement.
7. SOLUBILITY OF PALLADIUM CHLORIDE

COMPLEXES IN SUPERCRITICAL CARBON DIOXIDE
Complexes of palladium chloride with organic ligands have been synthesized as
described in [14]. The reason we have been led to utilize them, is that PdCl2 catalyst used in
conventional synthesis techniques, is insoluble in supercritical carbon dioxide.
Figure 9. Variation of the solubility of the benzonitrile complex of palladium chloride as a function of
the mass flow of SC-CO2 at 10 MPa and 308.15 K.
The products obtained were the benzonitrile PdCl2 (C6H5CN)2, styrene (C8H8PdCl2)2, and
cyclohexene (C6H10PdCl2)2 complexes. They were synthesized using carbon dioxide, with a
purity of 99.995 vol. % (CO2 from GOST (state standard) 8050-85, quality certificate No.
2052); palladium chloride of 99.99% purity, and pure benzonitrile, styrene, and cyclohexene,
pure for analysis, purity grade with at least 99.7% of major component.
The solubility of all the complexes was studied at 308.15, 318.15, and 328.15 K over the
pressure range from 10 to 32 MPa, with the experimental apparatus described in Figure 1,
under dynamic conditions.
All experiments were performed in two stages. In the first step, in the determination of
the solubility of anthracene, the variation of solubility as a function of the mass flow of
solvent was measured. At this stage, we determined the range of flow rates on which
equilibrium solute concentrations could be obtained. The results of these measurements for
benzonitrile complex are shown in Figure 9. Flow rates of SC-CO2 throughout the range of
0 to 0.5 g/min, give the condition to obtain the equilibrium concentrations. Similar curves
over the same range of carbon dioxide mass flows were obtained for the other two complexes.
In the second step, the solubility measurements were carried out for the palladium chloride
complexes under the conditions specified above.
The values of the solubility of palladium chloride complexes with organic ligands in
SC-CO2 are listed in Tables 3 to 5.
The solubility was described in terms of the model obtained from the condition of the
equality of the chemical potentials of the solute in the condensed and fluid phases. We have
assumed that the solute in the condensed phase was pure and incompressible, and the solution
in the fluid phase was diluted [15]:
PVm
ln( y)  ln(1  x2 )  ln( Psat / P)  ln( 2 ) 
RT , (1)
where y is the solubility of the solute in the supercritical fluid solvent, x2 is the solubility of
supercritical carbon dioxide in the solute, Psat is the saturated vapor pressure of the solute at
temperature T, P is the pressure in the system, Ф2 is the fugacity coefficient of the solute in
the solvent, Vm is the reduced molar volume of pure solute, and R is the universal gas
constant.
The fugacity coefficient of the solute in the fluid phase was calculated using a cubic
equation of state.
Peng-Robinson two parameter equation of state which is widely used for predicting the
solubility of heavy solutes in super critical gases, and provides reasonable accuracies to all
calculations of all fluid properties in natural gas processes, was found suitable for this
calculation:
RT a
P  2
V  b V  2bV  b 2 , (2)
where V is the specific volume, a and b are the Peng-Robinson equation parameters. This
equation only requires the critical properties and acentric factor for the generalization of
parameters.
Table 3. Variation of the solubility of palladium chloride benzonitrile complex in

supercritical carbon dioxide, along three isotherms as a function of pressure
T = 308.15 K T = 318.15 K T = 328.15 K

Solubility: y, Flow rate, P, Solubility: y, Flow rate, P, Solubility: y, Flow rate,
P, MPa
mole fraction g/min MPa mole fraction g/min MPa mole fraction g/min
10.0 0.000306 0.39964 10.0 0.000235 0.39978 10.0 0.000191 0.40031
11.0 0.000418 0.40222 11.0 0.000268 0.39909 11.0 0.000230 0.39926
12.5 0.000520 0.39978 12.5 0.000449 0.40038 12.5 0.000381 0.40152
14.0 0.000591 0.40113 14.0 0.000539 0.39691 14.0 0.000436 0.40303
15.0 0.000621 0.40010 15.0 0.000572 0.40124 15.0 0.000498 0.39950
17.5 0.000684 0.401134 17.5 0.000631 0.39958 17.5 0.000525 0.40031
18.5 0.000629 0.398578 20.0 0.000757 0.39863 20.0 0.000649 0.40038
20.0 0.000541 0.396634 22.5 0.000950 0.40207 22.5 0.000705 0.40103
22.0 0.000452 0.40567 25.0 0.000815 0.40323 25.0 0.000788 0.39759
25.0 0.000367 0.405878 27.5 0.000611 0.40274 27.5 0.000956 0.39964
27.0 0.000285 0.40206 30.0 0.000387 0.40099 28.5 0.001004 0.40331
30.0 0.000172 0.39980 32.5 0.000250 0.39825 30.0 0.000974 0.39996
32.5 0.000123 0.40498 32.5 0.000479 0.39895
Table 4. Variation of the solubility of palladium chloride styrene complex in

T = 308.15 K T = 318.15 K T = 328.15 K

Solubility: y, Flow rate, Solubility: y, Flow rate, Solubility: y, Flow rate,
P, MPa P, MPa P, MPa
mole fraction g/min mole fraction g/min mole fraction g/min
10.0 0.000398 0.39963 10.0 0.000274 0.39978 10.0 0.000202 0.40031
11.0 0.000427 0.40223 11.0 0.000287 0.39909 11.0 0.000235 0.39926
12.5 0.000486 0.39978 12.5 0.000306 0.40038 12.5 0.000253 0.40152
14.0 0.000532 0.40113 14.0 0.000368 0.39691 14.0 0.000291 0.40303
15.0 0.000547 0.40010 15.0 0.000390 0.40124 15.0 0.000307 0.39950
17.5 0.000598 0.40114 17.5 0.000430 0.39958 17.5 0.000345 0.40031
20.0 0.000723 0.39664 20.0 0.000510 0.39863 20.0 0.000397 0.40038
22.0 0.000642 0.40567 22.5 0.000648 0.40207 22.5 0.000468 0.40103
25.0 0.000539 0.40588 25.0 0.000827 0.40323 25.0 0.000655 0.39759
27.5 0.000505 0.40206 27.5 0.000695 0.40274 27.5 0.000801 0.39964
30.0 0.000456 0.39980 30.0 0.000637 0.40099 30.0 0.000937 0.39996
32.5 0.000392 0.40498 32.5 0.000595 0.39825 32.5 0.000757 0.39895
Table 5. Variation of the solubility of palladium chloride cyclohexene complex in

T = 308.15 K T = 318.15 K T = 328.15 K

Solubility: y, Flow rate, Solubility: y, Flow rate, Solubility: y, Flow rate,
P, MPa P, MPa P, MPa
mole fraction g/min mole fraction g/min mole fraction g/min
10.0 0.000332 0.39965 10.0 0.000255 0.39978 10.0 0.000162 0.40031
11.0 0.000365 0.40223 11.0 0.000269 0.39909 11.0 0.000184 0.39926
12.5 0.000406 0.39978 12.5 0.000296 0.40038 12.5 0.000232 0.40152
14.0 0.000465 0.40113 14.0 0.000356 0.39691 14.0 0.000252 0.40303
15.0 0.000492 0.40010 15.0 0.000380 0.40124 15.0 0.000276 0.39950
17.5 0.000591 0.40114 17.5 0.000424 0.39958 17.5 0.000318 0.40031
20.0 0.000652 0.39664 20.0 0.000510 0.39863 20.0 0.000374 0.40038
22.0 0.000669 0.40567 22.5 0.000661 0.40207 22.5 0.000493 0.40103
25.0 0.000460 0.40588 25.0 0.000715 0.40323 25.0 0.000654 0.39759
27.5 0.000351 0.40206 27.5 0.000571 0.40274 27.5 0.000749 0.39964
30.0 0.000325 0.39980 30.0 0.000507 0.40099 30.0 0.000678 0.39996
32.5 0.000251 0.40498 32.5 0.000461 0.39825 32.5 0.000623 0.39895
In order to calculate the solubility of solid complexes in SC-CO2, the binary interaction
parameters were correlated with the properties of pure substances. These parameters, which
take into account the special features of pair interactions between different molecules, were
calculated according to the Mukhopadhyay-Rao mixing rules [16], with the introduction of
mij empirical correction. Mukhopadhyay and Rao, in order to minimize the influence of the
cohesive energy parameter aij, due to the large asymmetry, incorporate a co-volume
dependency in the mixing rule for the cohesive energy parameter of the equation of state.
They assumed that, in dilute supercritical mixture, including molecules having large
differences of size, the probability of a molecule to interact with another in its vicinity,
depends on the fraction of the surface of the other molecule it will interact, rather than the
relative number of mole fraction. In their model, the repulsive forces become exceedingly
important in the quantification of the energy of interaction of large sized molecules.
To take into account the asymmetry and specificity, an inverse co-volume (bij)
dependency has been introduced in their mixing rule, for the attraction energy parameter aij.
The MR mixing rule was written as follows:
mij
b
a   yi y j aij  
b 
i j  ij  , (3)
The other quantities in Equation (3) are:
b   yi bi
i , (4)
aij  (aii a jj ) 1/ 2
, (5)
bij  (bii b jj )1/ 2

, (6)
The choice of mii = mjj = 1 reduces the sensitivity of the adjustable parameter mij, while
restricting the number of adjustable parameters to only one. Then mij was considered as an
adjustable parameters varying between 0.0 and 4.0. However an optimum value of 1.1 to 1.4
was found to give the best results for the systems considered in this analysis (see Table 7).
Furthermore, the fact that the mixing rule was aimed to be used for solid surface free energy
calculation gives it superiority over other one adjustable parameter mixing rule, as they were
planned to be used with any phase equilibrium calculations.
Here, yi and yj are the mole fractions of the ith and jth components of the mixture,
respectively, in all the equilibrium phases.
For pure compounds, Peng-Robinson parameters are combinations of their critical
pressures and temperatures
ai  0.45724 R 2Tc2 i T  / Pc , (7)
bi  0.0778 RTc / Pc , (8)

2
   T 1/ 2 
 
 i T   1  0.37464  1.54226 i  0.26992 i 1    
2 
  Tc  

   , (9)
  1.000  log10 Psat / Pc Tr 0.7 (10)
where Pc, Tc, ω, and Psat are respectively the critical pressure, the critical temperature, the
acentric factor and the saturation pressure at Tr = 0.7 of the ith component.
Critical parameters of the complexes solid reported in this study were set equal to the
critical parameters of pure palladium; because currently no experimental data have been
reported in the literature, since these complexes decompose at high temperature. Moreover,
no theoretical model is available for the determination of the critical parameters of these
complexes, as palladium critical parameters are an order of magnitude larger than the critical
parameters of the organic ligands present in the complex. Palladium critical parameters were
calculated according to the procedure described in [17]; they are listed in Table 6. The
adjustment of binary interaction empirical parameter mij is determined at a fixed temperature,
by fitting experimental solubility data and minimizing an error function F. More details for
the computation can be found in the paper of Bilalov et al. [19].
1 n  yicalc  yiexp 
F 
n i 1  yiexp 

, (11)
where n is the number of experimental data points and y is the solubility of the solid in the
supercritical phase.
Table 6. Solute and solvent critical parameters
Critical parameters Palladium CO2 [18]

Tcr, K 4060 304.1282
Pcr, MPa 8.104016 7.3773
Vcr, m3/kg 0.005 0.0021386
The physical properties and vapor pressure parameters for pure compounds that are
necessary as input data to the program were taken from [19]. In this book different method
are reported for the calculation of the vapor pressure and we use the method of Li-Kesler.
The results of calculations of solubility of complex are presented in Figures 10-12. In Table 7
are reported the empirical binary interaction parameters for the systems under consideration.
The error in the description of the solubility of the complexes varies from 14 to 32% that
is much larger than the error in the solubility measurements. The quality of the description of
the solubility of the complexes in SC-CO2 decreases as the temperature increases, primarily
due to the imperfection of the model, particularly as applied to metals and their compounds,
and to a large degree, because of arbitrary selection of the critical parameters of the solutes.
Figure 10. Solubility of palladium chloride benzonitrile complex in SC-CO2 at (1) - 308.15 K, (2) -
318.15 K, and (3) 328.15 K; (4-6) - description (calculations).
Figure 11. Solubility of palladium chloride styrene complex in SC-CO2 at (1) - 308.15 K, (2) - 318.15
K, and (3) - 328.15 K; (4-6) description (calculations).
Figure 12. Solubility of palladium chloride cyclohexene complex in SC-CO2 at (1) - 308.15 K, (2) -
318.15 K, and (3) - 328.15 K; (4-6) - description (calculations).
Table 7. Binary interaction coefficients
Supercritical carbon dioxide-organometallic Temperature, Binary interaction coefficient,

complex system K mij
308.15 1.2795
Benzonitrile
318.15 1.3270
complex
328.15 1.2432
308.15 1.2156
Cyclohexene
318.15 1.1631
complex
328.15 1.3037
308.15 1.2781
Styrene
318.15 1.3045
Complex
328.15 1.3882
REFERENCES
[1] Bilalov, T. R., Gumerov, F. M., Gabitov, F. R., Kharlampidi, Kh. E., Fedorov, G. I.,
Sagdeev, A. A., Yarullin, R. S., Yakushev, I. A. The Synthesis and Regeneration of
Palladium Catalysts with the Use of Supercritical Carbon Dioxide. Russian Journal of
Physical Chemistry B, 2009, 3, 80-92.
[2] Ethylene Production in the CIS Reactors and Catalysts [electronic resource]. - Mode of
access: http://www.newchemistry.ru/letter.php?n_id=105&cat_id=105.
[3] Shvets, V. F. Introduction to the Chemistry of Catalytic Reactions. Soros Educational
Journal, 1996, 6: 33-40.
[4] Sarkany, A. Formation of C4 Oligomers in Hydrogenation of Acetylene over Pd/Al2O3
and Pd/TiO2 Catalysts. Reaction Kinetics and Catalysis Letters, 2001, 74, 2: 299-307.
[5] Temkin, O. Catalytic Chemistry. Soros Educational Journal, 1996, 1: 57-65.
[6] Gumerov, F. M., Sabirzyanov, A. N., Gumerova, G. I. Sub- and Supercritical Fluids in
Processes of Polymer Processing, FEN publisher, Kazan, 2007: p. 328. [in Russian].
[7] Osada, M., Hiyoshi, N., Sato, O., Arai, K., Shirai, M. Reaction Pathway for Catalytic
Gasification of Lignin in Presence of Sulfur in Supercritical Water. Energy and Fuels,
2007, 21: 1854-1858.
[8] Osada, M., Hiyoshi, N., Sato, O., Arai, K., Shirai, M. Subcritical Water Regeneration of
Supported Ruthenium Catalyst Poisoned by Sulfur. Energy and Fuels, 2008, 22: 845-
849.
[9] Aim, K. Solubility of Solids and Liquids in Supercritical Fluids. The Experimental
Determination of Solubilities, 2002, 5.1:, 491-553.
[10] Encyclopedia “Krugosvet”: Catalysis [electronic resource]. - Mode of access: http://
www.krugosvet.ru/articles/43/1004365/print.htm.
[11] Kolesnikov, I. M. Catalysis and Catalysts Production. Technology publisher, Moscow,
2004.
[12] Anitescu, G., Tavlarides, L. L. Solubility of Solids in Supercritical Fluids. New
Quasistatic Experimental Method for Polycyclic Aromatic Hydrocarbons (PAHs) +
pure fluids. The Journal of supercritical fluids, 1997, 10: 175-189.
[13] Nelsen, F. M., Eggertesen, F. T. Determination of the Surface Area. Adsorption

Measurements by Continuous Flow Method. Analytical Chemistry, 1958, 30, 8: 1387-
1390.
[14] Kharasch, M. S., Seyer, R. C., Mayo, F. R. Coordination Compounds of Palladium
Chloride J. Am. Chem. Soc. 1938, 60: 882-884.
[15] Ashour, I., Almehaideb, R., Fateen, S. E., Aly, G. Representation of Solid-Supercritical
Fluid Phase Equilibria Using Cubic Equations of State. Fluid Phase Equlib., 2000, 167,
1; 41-61.
[16] Mukhopadhyay, M., Raghuram Rao, G. V. Thermodynamic Modeling for Supercritical
Fluid Process Design. Ind. Eng. Chem. Res. 1993, 32: 922-930.
[17] Nikolaev, O. S. Critical State of Metals, Lenand publisher, Moscow, 2006 [in Russian].
[18] Reid, R. Properties of Gases and Liquids. McGraw-Hill publisher, New York, 1987;
Khimiya publisher, Leningrad, 1982.
[19] Bilalov, T. R., Gumerov, F. M. The Manufacturing Processes and Catalyst
Regeneration. Thermodynamic Basis of Production Processes and Regeneration of
Palladium Catalysts Using Supercritical Carbon Dioxide. LAP LAMBERT Academic
Publishing GmbH and Co. KG., Dudweiler Landstr., Germany, 2011: p. 153.
Chapter 2
REGENERATION OF NICKEL ON KIESELGUHR

CATALYST USED IN THE PROCESS OF SEPARATION
OF ACETYLENE COMPOUNDS FROM ISOPRENE
BY SUPERCRITICAL СО2 EXTRACTION
R. F. Gallyamov1, А. А. Sagdeev1, F. M. Gumerov2,*

and F. R. Gabitov2
1
Nizhnekamsk Institute for Chemical Technology, Nizhnekamsk, Russia
2
Kazan State Technological University, Kazan, Russia
ABSTRACT
The nature of deactivating deposits forming on the supported “nickel on kiеselguhr”
catalyst in the course of hydration of unsaturated compounds is analyzed. The possibility
of regeneration of the catalyst using pure supercritical carbon dioxide and SC-CO2
modified with polar additive (3 wt.% methanol) is investigated at 343 and 423 K, in the
pressure range 10-30 MPa. The kinetic features of the regeneration of the catalyst with
SC-CO2 is studied. A comparison of activities of freshly prepared, spent and regenerated
with SC-CO2 catalyst samples, showed that the method suggested was highly competitive
compared to conventional regeneration techniques.
Keywords: acetylene, isoprene, catalyst regeneration, catalyst activity, nickel on kiеselguhr

catalyst, supercritical carbon dioxide
*
24 R. F. Gallyamov, А. А. Sagdeev, F. M. Gumerov et al.
1. INTRODUCTION
Ethylene is a monomer used for the preparation of a large number of polymers. It is
generally obtained by hydrocarbon pyrolysis or steam cracking processes. Product streams of
liquid or liquefiable olefins and diolefins are generally contaminated with small amounts of
acetylenic impurities. For example, the ethylene/ethane fraction in an ethylene plant typically
contains 0.5-2.0 wt. % acetylenic impurities. Such acetylenic contamination is undesirable
because acetylene tends to poison the catalysts that are used to convert ethylene to
polyethylene. Acetylene also can form metal acetylides which are explosive and which may
contaminate the equipment that is used to process such product streams. The contents of
acetylene which are tolerated in ethylene for use in the production of polymers are generally
less than 10 ppm, usually less than 1 ppm.
Acetylenic impurities can be selectively hydrogenated and thereby removed from such a
product streams by passage of the product stream over an acetylene hydrogenation catalyst, in
the presence of hydrogen; however, the hydrogenation process usually results in the
deposition of a green oil on the catalyst which deactivates the catalyst.
Catalysts suitable for hydrogenation of acetylene must meet high requirements in terms
of their selectivity and activity, since the hydrogenation is to take place without loss of
ethylene.
One technique used to remove acetylene of ethylene is to selectively hydrogenate it to
ethylene, in the presence of a nickel based catalyst, supported on a refractory support such as
Kieselguhr. Heterogeneous supported nickel catalysts, containing 2.5% to 20% of nickel
metal, are widely used for various industrial processes in chemical industry as hydrogenation
reactions, hydrotreating, steam-reforming and methanation. Nickel is cheap and sufficiently
active, and allows suitable catalysts to be produced economically. The nickel catalyst is well
known for its superior hydrogenation abilities, and it is commonly used in industry. This
catalyst was also used to separate the acetylene compounds from isoprene, by selective
hydrogenation at Nizhnekamskneftekhim JSC.
These catalysts have specific efficiency and duration, which determine the level of
chemical technologies. These catalysts deactivate over time due to deposition of coke on their
surface. When the activity of a catalyst drops below an acceptable level, the catalyst must be
regenerated and reused. Several alternative methods such as disposal in landfills, recovery of
metals, regeneration/rejuvenation and reuse, and use as raw materials to produce other useful
products are available to the refiners to face the problem of spent catalyst. The choice
between these options depends on the technical feasibility and economic considerations.
However, when in situ regeneration is not possible, or even after a few cycles of
regeneration and reuse, the catalyst activity may decrease to very low levels, so that further
regeneration might not be economically feasible. In such cases, spent catalysts tend to be
discarded as solid wastes. Due to increasing environmental concerns and legislation regarding
the disposal of hazardous spent catalysts, companies and countries are being forced to process
their own waste products and residues.
Burial catalysts in landfills are unacceptable, as the metals present in the catalysts can be
leached into the groundwater, causing an environmental catastrophe. In addition to the
formation of leachate, the spent catalysts, when in contact with water, may release toxic gases
as well. Due to strict environmental regulations on spent catalyst handling and disposal,
Regeneration of Nickel on Kieselguhr Catalyst … 25
research on the development of processes for the recycling and reuse of spent catalysts waste,
has received considerable attention. Metal recovery from nickel catalyst is also extremely
important from an economic point of view, as the cost and demand of nickel has been
increasing significantly; some processes were developed for the recovery of nickel from spent
catalyst. These research works focuses on the recovery of nickel using conventional acid
leaching, chelation route and ultrasonication. The nickel thus recovered can be recycled for
the preparation of fresh catalysts.
Therefore, off-site catalyst regeneration is one of the main issues in providing good
technical and economic efficiency of the vast majority of oil refining and petrochemical
processes.
At chemical plants, the coke deposited on an acetylene hydrogenation catalyst is
traditionally removed by an oxygenation step, followed by hydrogen reduction, which
consists in the controlled burnout of coke by gaseous mixtures containing oxidizers (oxygen)
at catalysis temperature or higher. However, the regeneration with oxygen containing gas or
thermal treatment with direct steam are tedious, time and energy consuming processes, and
results in environmentally undesirable emissions. Furthermore, if the regeneration is
performed in situ, the concentration of oxygen in the regeneration gas stream must be
regulated carefully, in order to avoid reactor temperature run-away. It would be advantageous
if acetylene hydrogenation catalysts could be regenerated using a method which did not
require such time consuming purging and monitoring.
In our view, one promising method for regenerating catalysts is a supercritical fluid
extraction (SCFE). The supercritical fluid (SCF) technology has significant advantages over
traditional methods. In this case, the working media in the supercritical fluid state uniquely
combines solubility, traditionally inherent to liquid organic solvents, and the low viscosity
and high diffusion characteristic of gaseous fluids. The last provides high mass transfer
characteristics of the processes involving supercritical fluids.
Despite the fact that there is a wide range of compounds, in the supercritical fluid state,
used as SCF solvent and extractant, nevertheless the supercritical carbon dioxide (SC-CO2) is
the most popular and widely demanded. This is because CO2 has convenient critical
parameters (Tc = 304.14 K, Pc = 7.378 MPa), it is inert, non-flammable and non-explosive, as
well as eco-friendliness of the product obtained and the production as a whole.
Regeneration process of catalysts and adsorbents using supercritical fluids in comparison
with the traditional approach is milder process conditions, high efficiency and lower energy
costs. Consequently catalysts under the new approach go through more regeneration cycles.
The scientific literature shows the interest to this process both the researchers, and the
industrial achievements of this SCF method.
The purpose of this study was to explore the possibility of regeneration of spent nickel on
kieselguhr catalyst from the company of “Nizhnekamskneftekhim” in a supercritical carbon
dioxide medium.
In order to regenerate the catalyst, the amount of coke formed on the surface of nickel on
kieselguhr catalyst was determined by the integrated thermal analysis method, consisting of
thermogravimetric and differential thermal analysis (TG-DTA) in the temperature range from
293 to 1123 K. The regeneration process was carried out in pure supercritical carbon dioxide
and supercritical carbon dioxide with an optimum concentration of 7 wt. %, of chloroform,
methanol, acetone and dimethyl sulfoxide. The highest degree of extraction of deactivating
compounds was obtained using dimethyl sulfoxide as a co-solvent.
2. PROCESS OF THE SEPARATION OF ACETYLENE COMPOUNDS FROM

AN ISOPRENE MIXTURE; CHARACTERISTICS OF THE SPENT
CATALYST; DESCRIPTION OF A CONVENTIONAL
PROCESS FOR ITS REGENERATION
The catalytic hydrogenation technique, along with other important processes of organic
chemistry, is widely used in the chemical and petrochemical industries, as well as in scientific
research for the synthesis of various organic compounds. The introduction of hydrogenation
in engineering has contributed to promoting large-scale development of processes for the
synthesis of the upgrading of fuel from carbon oxides and a number of reduction reactions.
The catalysts commonly used in the hydrogenation reaction, traditionally belong to the
group VIII elements of the periodic table of Mendeleev. The nickel deposited on a porous
support like pumice, magnesia, kieselguhr, etc. is generally used as catalyst in the
hydrogenation process of unsaturated hydrocarbons [1].
In particular, the nickel on kieselguhr catalyst that we have studied is used in the
petrochemical and chemical industry for the selective hydrogenation of acetylene with
impurities in diolefins, such as 1,3-butadiene, methyl-allene, isoprene and piperylene
compounds, and carbonyl impurities in benzene and substituted benzene compounds [2].
This catalyst was also used to separate acetylene compounds from isoprene by selective
hydrogenation at Nizhnekamskneftekhim JSC [3].
The reaction of hydrogenation of acetylenic compounds primarily represented as
isopropyl acetylene and tert-butyl acetylene, to amylene proceeds with the nickel catalyst in
the course of operation [1].
For instance, if we considered the reaction of conversion of isopropyl acetylene in
isoamylene:
Ni
СН3  СН  С ≡ СН + Н2  СН3  СН  СН = СН2
СН3
СН3
isopropylacetylene isoamylene
Under these conditions, there is also a secondary reaction of hydrogenation of isoprene to

isoamylene, which goes on with the main reaction:
Ni
СН2 = С  СН = СН2 + Н2  СН3  СН  СН = СН2
СН3
СН3
isoprene isoamylene
The catalyst has a cylindrical shaped and is made of green tablets with a diameter of 4 to
5 mm and a height of 4 to 6 mm. It was produced by deposition of metallic nickel and nickel
oxide on kieselguhr with the addition of graphite and after the granular powder was
compressed to high pressure to make the particles stick together.
Hydrogenation process is performed by means of electrolytic hydrogen, at a temperature
of 293 K, and a pressure of 0.15 MPa, in the liquid phase on a fixed bed catalyst.
The catalyst support is kieselguhr also known as diatomaceous earth or diatomite; it is a
naturally occurring siliceous sedimentary rock, which was easily crushed into a white to off-
white fine powder. Diatomaceous earth consists mainly of fossilized remains of diatom shells,
which gives to the porous support for chemical catalysts a high porosity (50 to 80%) and a
low density. This low density can create bonding problems, due to the weak, non-durable
surface that results. For this reason, diatomite is not yet widely used as a metal catalyst carrier
in the form of large tablets. The composition of kieselguhr is given in Table 1.
Most varieties of kieselguhr are powders, but there are also granular grades. All varieties
belong to two categories according to the size of the specific surface area and average pore
diameter.
One is the raw kieselguhr powder, with a specific surface area of 15 to 40 m2/g, and a
pore size of 0.2 to 0.7 m. The other is non-calcined kieselguhr, prepared by drying at
T < 673 K, with a specific surface area of 2 to 6 m2/g, and a pore size of 2 to 5 m (a smaller
specific surface area corresponds to a greater pore size). Natural kieselguhr also includes a
number of diameter sizes of pore (average <15 m), which disappear upon calcinations.
Kieselguhr is useful for support as it has good thermal and chemical stability, combined with
a moderate specific surface area and relatively large pores facilitating the transport of
reactants [4].
In Table 2, the physical and chemical characteristics of nickel on kieselguhr catalyst used
at Nizhnekamskneftekhim J S C are presented [2].
An important factor in the isoprene hydrogenation process is the residence time of the
reactants in the catalyst zone, the so-called contact time, which is determined by the
conditional space velocity (SV). The space velocity refers to the quotient of the entering
volumetric flow rate of the reactants divided by the volume of the reactor (or the volume of
the catalyst bed):
VRe act.
SV 
V , (1)
where SV is the ratio between the volumetric flow rate of hydrogen reactant, adjusted to a set
of standard conditions, entering the reactor VReact, to the volume of the saturated catalyst V. It
indicates the number of reactor volumes of hydrogen, which can be treated in a unit of time. It
is generally regarded as the reciprocal of the reactor space time (i.e., SV = 1/).
The change of volume rate modifies the degree of hydrogenation of isoprene. The
temperature, the pressure and the catalyst selectivity have a great influence on the
hydrogenation process. Increasing the reactor temperature results in a decrease of the
selectivity of the catalyst and the rise of secondary hydrogenation reactions which stimulated
intensive coke formation on the catalyst surface [5, 6].
Table 1. Composition of kieselguhr
Compounds Composition
SiO2 70 to 90 wt. %
Fе2O3 2 to 10 wt. %
Al2O3, СаO, МgО 4 wt. %
Another reason for the coke formation is that the catalytic refining and petrochemical
processes occur under conditions where the hydrocarbons are thermodynamically unstable. In
the absence of kinetic constraints, they would be completely converted into graphite and
hydrogen. This special condition governs the general tendency to coke formation in
hydrocarbon treatment processes [7].
As part of this implementation, nickel on kieselguhr catalyst loses its activity and the
process of hydrogenation of isoprene deteriorates. In this case, the reactor is shut down, the
hydrogenation process is interrupted and the reactor is restarted with a new catalyst or a
regenerated catalyst with a steam-air mixture [3].
The catalyst activity may decrease to such an extent that its continual use becomes
economically not viable. The most established method of regeneration involves the oxidative
removal (by burn-off), of carbonaceous deposits, usually referred to as coke, which deposited
on the catalyst surface during the process. In general, during the first stages of regeneration,
dilute air is used as oxidation medium for safety reasons. The final stages of the process of
regeneration take place after the most reactive components of coke has been removed and can
be complete using air or gas mixtures containing oxygen. However, the additional cost of
these changes must be compensated by an improvement in regeneration efficiency.
Let us briefly recall the significant complexity of the regeneration mechanism:
In the presence of oxygen under standard regeneration conditions, both inorganic part and
organic part of the spent catalyst are oxidized. The first step involves the burn-off of the bulk
of carbon. For this purpose, the catalyst is treated with a gas mixture containing preferably 0.5
to 2.0 (vol. %) of О2, 0.1 to 5.0 (vol. %) of Н2О and 0.001 to 0.25 (vol. %) of halogenated
compounds (CCl4, chlorinated ethane and methane), the rest is an inert gas.
The second step involves treating the catalyst with a gas mixture, which contains oxygen,
to remove residual carbon and to ensure the conversion of metals to oxides. Under this
experimental condition, the oxygen content in the gas mixture passing through the catalyst is
higher than in the burn-off step, preferably 4 to 25 (vol. %). The mixture also contains 0.1 to
5.0 (vol. %) of Н2О, and 0.001 to 0.25 (vol. %) of halogenated compound and an inert gas.
Table 2. Physical and chemical characteristics of fresh catalyst
Mass fraction of nickel, less than 54 wt.%

Mass fraction of sulphide sulfur, less than 0.38 wt.%
Activity (specified) determined by pseudo-cumene hydrogenation, more than 65%
Selectivity determined by acetylene hydrogenation, no less than 73%
Bulk density, no less than 1150 kg/m3
Longitudinal mechanical compressing strength, average, more than minimum, 0.415 kg/mm2
more than 0.260 kg/mm2
In the third stage the catalyst is purged with air containing 1.0 to 3.0 (vol. %) of Н2О and
0.001 to 1.5 (vol. %) of HCl. The objective of this procedure is to bring the halogen content in
the catalyst to 0.5-1.5 (vol. %);
Finally, the catalyst is flushed with nitrogen, at temperatures from 773 K to 873 K,
followed by a step of reduction with hydrogen, for a period of 0.5 to 2.0 hours, at
temperatures from 723 to 873 K [3].
This described catalyst regeneration process is a long and expensive process, and has the
following disadvantages [8]:
a) The possibility of local overheating of the catalyst, as well as incomplete removal of

carbon due to the uneven distribution of the regeneration medium in the catalyst bed
(the gas flowing in channels).
b) The irreversible deactivation of the catalyst when steam is used at high temperatures
for the regeneration.
c) It is doubtful that during industrial regeneration, a 100% elimination of carbon,
nitrogen and sulfur is achieved. Some studies have confirmed that the residual sulfur
in regenerated catalyst was a sulfate form, which remained in the catalyst after
successive sulfiding processes. The elements that are left inside have harmful effects
on the activity of catalyst recovery.
d) The processing time, in some cases, is long and can take anywhere from five days to
five weeks;
e) The uncertainty of the effectiveness of the regeneration of the catalyst has an effect
on the estimation of the duration of the subsequent cycles.
Considering all the disadvantages of the traditional method, the regeneration of catalysts
by supercritical fluid extraction (SCFE) seemed to be very promising. The supercritical fluid
(SCF) technologies have significant advantages over traditional methods. In this case, the
working fluid being in a supercritical fluid state, uniquely, combines the power of dissolution,
which is traditionally inherent in liquid organic solvents, as well as a low viscosity and high
diffusivity exclusive to gaseous media. The latter provides high mass transfer characteristics
of processes involving supercritical fluids [9].
Although a wide range of substances in a supercritical fluid state is used as an extraction
solvent, however supercritical carbon dioxide (SC-СО2) is the most popular and widely used.
This is due to the appropriate critical parameters of СО2 (Тc = 304.29 K, Pc = 7.378 MPa), its
inertia, its fire and explosion safety, as well as its friendliness for the environment, both in the
product obtained and the production as a whole.
3. MATERIALS, EQUIPMENT, APPLIED RESEARCH METHODS

The possibilities for using supercritical fluid extraction process, for the regeneration of
catalysts and absorbents, are studied today in many research laboratories, both in Russia and
abroad. SCFE process offers unlimited possibilities for the extraction and dissolution of
different chemical compounds in porous materials.
The processes of catalyst and adsorbent regeneration by supercritical fluids are

characterized by milder process conditions, high efficiency and lower energy consumption
compared to the traditional approach. Accordingly, the catalysts support a larger number of
regeneration cycles in this new approach [10]. The substantial scientific literature on the
subject shows both interest of researchers in this process [11-13], and the industrial
achievements of the SCF method [14, 15].
An experimental facility was built as part of this study (Figure 1), which allows both the
implementation of the method of measurement of solubility, and the set-up to regenerate
catalysts by supercritical fluid extraction, either with pure or modified fluid agent of
extraction. Changing the nature of the extractant is carried out by adding a co-solvent in SC-
CO2, before it is introduced directly into the extraction cell [19].
Figure 1. Schematic diagram of the extraction plant: (1) - СО2 bottle; (2) - СО2 feed pump; (3) -
refrigeration unit; (4) - condenser; (5) - co-solvent feed syringe pump; (6) - co-solvent vessel; (7) -
check valve; (8) - extraction cell; (9) Heat exchanger; (10) - three-way valve; (11) - needle valve; (12) -
tubular electric heater; (13) - restrictor (with throttling device functions); (14) - standard pressure
gauge; (15) - fine filter; (16) - extract collector; (17) - thermocouple [20].
During the experiment, CO2 is introduced from the bottle, through the fine filter and
condenser, with the high pressure fluid pump (brand LIQUPUMP 312/1), which provides a
fixed flow rate of liquid carbon dioxide in the range of 0.01 to 9.99 cm3/min, with a pressure
of up to 40 MPa.
For normal operation of the pump, supply of liquid carbon dioxide to the suction circuit
must be ensured. Gas liquefaction occurs directly in the condenser and in the pump and is
powered by the circulation of refrigerant in the cooling jacket of the pump and an annular
condenser. The temperature at which the cooling unit cools the coolant (258 K) is controlled
by a chromel-copel thermocouple mounted in the condenser.
The co-solvent is provided to the common backbone, via a syringe pump (model SFE–
400), from the vessel through the three-way valve. The pump is used to regulate the supply of
co-solvent in the range of 0.01 to 11.0 cm3/min, which gives the desired modifier
concentration (3 to 10 wt. %), in SC-CO2.
Check valves are used to prevent the return of СО2 and co-solvent to the pump.
A mixture carbon dioxide and co-solvent is compressed by the pump, passes through the
capillary tube and through the heat exchanger, where it is heated above the critical
temperature of carbon dioxide. After that, modified SC-СО2 enters the extraction cell
mounted within the heat exchanger, wherein an amount of catalyst was loaded. The heat
exchanger is a thick-walled copper tube with a heating element, in the form of a coaxial wire
made of steel, wound around it. The temperature of the extraction cell is maintained with an
accuracy of ± 0.25 K, with an electronic meter control device (2TRM1 trademark). Chromel-
copel thermocouples mounted at the ends of the cell are used to control the temperature. The
accuracy of temperature measurements is estimated to be ± 0.05 K.
A modified SC-СО2 with substances dissolved therein, flows from the extraction cell into
the restrictor, wherein the drop in pressure occurs, and the substances dissolved in SC-СО2
are deposited in the extract collector.
To avoid a premature release of substances dissolved in the fluid inside the capillary tube,
a temperature equal to the extraction temperature is maintained, by means of a tubular electric
heater in the region between the cell and the restriction element. The catalyst is weight before
and after the experiment to determine the changes in its mass and the number substances
extracted by deactivation. The mass flow rate of the solvent during the regeneration process is
maintained in the range of 2.0 to 2.5 g/min.
The amount of coke formed on the surface of nickel on kieselguhr catalyst was
determined by the integrated thermal analysis method. Simultaneously thermogravimetric and
differential thermal analysis (TG-DTA) are carried out, using a derivatograph manufactured
by MOM (Hungary), in the temperature range from 293 to 1123 K, in dish-shaped platinum
holders open in the air; the sample size is 600 mg. The absolute error in the determination of
the temperature is ± 5 K, and the relative measurement error of the mass, at a given sensitivity
of 0.2 mg is ± 0.5%.
A sample of the deactivated catalyst weighing 10 g, was dissolved in 25 cm3 of
chloroform in order to perform infrared spectroscopic studies. After 2 hours, the extract
which has captured chloroform, is transferred to a plate of NaCl, and a thin film of the test
substance is obtained after evaporation of the chloroform. The plate is placed in the FTIR
spectrophotometer Vector 33, equipped with a frustrated multiple internal reflectance
attachment, and spectra in the wavelength range of 600 to 4000 cm-1 were recorded at room
temperature for 1 min.
Suspensions (slurries, pastes) are dispersed in the paraffin oil to obtain the spectra of the
catalysts themselves. Paraffin oil is a mixture of normal and saturated hydrocarbons with an
average composition of C25.
The solution should be substantially free of aromatic and unsaturated hydrocarbons and
other impurities, and have a sufficient viscosity and a suitable refractive index, in order to
obtain satisfactory solid spectra.
The suspension is prepared by grinding and mixing the catalyst in paraffin oil, until a
sufficient dispersion is achieved. The desired thickness is obtained by squeezing KBr plates,
between which a layer of paste has been inserted. The thickness of the paste layer must be the
same for different catalyst samples under test. Through the windows set on a cell metal stand,
which is placed on the FT-IR Vector 33 spectrophotometer and the spectrum sample is
recorded. The recording conditions of the IR spectra of the catalysts themselves were similar
to those studies on chloroform extracts.
The extraction of deactivated components was carried out in a Soxhlet apparatus, using
the method described in [21], for the quantitative analysis thereof; the weight of the catalyst
was 5 g, the amount of extractant (acetone) was 20 cm3, and the extraction time was 1 h. The
content of the extract components was determined by gas-liquid chromatography, using a
“Crystal-Lux 4000” apparatus, with a flame ionization detector.
The analytical conditions were the following: the flow rate of the carrier gas (hydrogen)
was 1 cm3/min; the heating rate was 10 K/min, in a temperature range from 313 to 473 K; the
length of the capillary column was 50 m, the capillary diameter was 0.32 mm, the thickness
of the stationary phase (polyethylene glycol) was 1.2 microns.
Identification of the components was performed using a DSQ gas chromatograph/mass
spectrometer (Thermo Electron Corporation, US) and Xcalibur 1.4 software, under similar
conditions to those of the chromatographic analysis (a length column of 50 m, a capillary
diameter of 0.32 mm).
A comparison of the activity of fresh, used (coked) and regenerated catalyst samples in
different ways, were carried out following the model reaction of hydrogenation of ethylene, in
the С2 hydrocarbons mixture, at the temperature 323 K.
The moisture content was determined by the weight loss of the sample during drying in
an oven at 378 ± 5 K.
The catalysts were analyzed using a micro catalytic pulsed unit (Figure 2), consisting of a
LHM-80M chromatograph and a reactor made of stainless steel, and having an inner diameter
of 6 mm and a length of 140 mm. The chromatograph is equipped with a column of 2 m in
length (5), in order to separate hydrogen, methane, ethane, ethylene, and with an internal
diameter of 3 mm, filled with γ-Al2O3 and 7 wt. % NaHCO3.
Figure 2. Diagram of a pulsed microcatalytic experimental unit: (1) - gas processing device; (2) -
injection valve with a metering volume; (3) - microreactor with electric heater; (4) - temperature
controller; (5) - chromatographic column; (6) - thermal conductivity detector; (7) - thermocouple [12].
The analysis is performed in a flow of helium as carrier gas (~30 cm3/min) and at a
column temperature of 343 K.
The reactor (3) has a thin-walled sheath (0.1 mm), the thermocouple (7) (chromel-copel),
is located just beneath the catalyst bed. The reactor is integrated into a brass unit, around the
cylinder; an electric coil is wound with uniform heating purposes. The temperature gradient in
the middle portion of the reactor, over a length of 50 mm, at 373 K does not exceed 2 K. The
measuring thermocouple (7) simultaneously controls and maintains the set point of the
temperature of the reactor, by means of the thermo-regulator (4). The accuracy of the
temperature measurement at 673 K is ± 2 K. The thermocouple was calibrated at the boiling
point of water and the melting points of tin, lead, cadmium and zinc.
The above setup is used both for the pretreatment of the catalyst (hydrogen recovery) and
for testing its activity.
The catalyst activity was measured by the degree of hydrogenation of ethylene to ethane,
with the pulsed supply of the mixture of 50% ethylene + 50% of hydrogen, in the carrier gas
stream, via a second upstream in the microreactor.
A catalyst test sample (~0.07 g), having a particle size of 0.2 to 0.5 mm, is mixed with
pure γ-Al2O3, in a ratio such that the total volume is 0.5 cm3. The catalyst is poured into the
central part of the microreactor (3); a junction of the thermocouple of measurement and
regulation (7) connected to the thermoregulator (4) is located just below. In addition, the
reactor is charged with heat-transfer medium (fused silica particles) up to the top, for
additional heating of the inflowing gaseous stream.
The temperature in the microreactor is increased to 673 K, and the catalytic reduction is
carried out using hydrogen pulses, injected through the injection valve (2). It can be checked
by the height of the negative peak of the hydrogen, at the cessation of hydrogen uptake, after
starting a certain number of pulses. Thereafter, the reactor temperature is reduced to 323 K,
and ethylene hydrogenation is performed with pulses of an equimolecular mixture of
hydrogen, introduced via the six-way injection valve.
The volume of pulses sent both in the reduction of the catalysts and investigation of their
activity) was about 2 cm3. Feed pulses were stopped after reaching a stable conversion of
ethylene to ethane.
Four catalysts were tested: the source (freshly prepared), spent and two regenerated with
supercritical carbon dioxide. One of the samples was regenerated with pure SC-СО2, and the
other one was regenerated with SC-СО2 modified with 3 wt. % of methanol.
4. REGENERATION OF NICKEL ON KIESELGUHR CATALYST USED

IN THE PROCESS OF SEPARATION OF ACETYLENE COMPOUNDS
FROM ISOPRENE BY SUPERCRITICAL CО2 EXTRACTION
The amount of coke deposits, formed on the surface of the nickel on kieselguhr catalyst,
was determined by the integrated method of thermal analysis and simultaneously by
thermogravimetry and differential thermal analysis (TG-DTA). Integrated thermal analysis
data are shown in Figure 3. Heating the coked catalyst sample leads to gradual reduction of its
weight, accompanied by one endothermic and two exothermic effects. During the
endothermic effect between 373 K and 393 K, weakly bound water and hydrocarbons of low
boiling point are removed. Exothermic effects (maxima at 513 K and 1073 K) indicate the
start of oxidation processes. The presence of these two effects suggests heterogeneity of the
deposits. The maximum weight loss of deactivated catalyst is observed at temperatures from
403 K to 873 K, as well as from 973 K to 1123 K. The total amount of condensation products
reaches 22.4 wt. %. The data of condensation products obtained by IR spectroscopy and
thermal analysis methods are shown in Table 3. The analysis of IR spectra of the extract of
spent catalyst in chloroform (Figure 4) showed that the coke deposits are mainly those of the
reaction products. There are isoprene oligomers, cis- and trans-isoamylenes and their
oxidation products.
Figure 3. TG-DTG curves of deactivated nickel on kieselguhr catalyst: (1) - Т (temperature variation);
(2) - DTG; (3) – TG.
Figure 4. IR spectrum of nickel on kieselguhr catalyst deposits.

Table 3. Data from the joint analysis of deactivated catalyst by

IR spectroscopy and TG-DTA [20]
Temperature, K Name Extract, wt.%

<473 Volatile components 5.8
473-613 Alkylbenzenes 5.8
613-873 Oxidized form of oligomers 5.0
873-993 Semi-coke 0.8
993-1123 Medium-temperature coke 3.3
>1123 High-temperature coke 1.7
Table 4. Results of the analysis of the extract of catalyst by joint gas chromatography
and mass-spectrometry [20]
Extract Content Extract, wt. %

Extract of the spent catalyst Hexane 7.8
DMFA 4.78
Toluene 8.4
Isopreneoligomers
55.4
(С11Н22–С15Н30)
Paraffins 20-25
Extract of the catalyst regenerate
Hexane 0.34
during SC-CО2 + 3 wt. % methanol
Toluene 0.56
DMFA 3.53
Methanol 60.1
Hydrocarbons (С7Н14) 32.6
Extracted compounds after the
Hexane 0.17
regeneration process
Toluene 0.8
DMFA 0.593
Isopreneoligomers (С11Н22–С20Н42) 68.156
Paraffins 29.82
The wave numbers in the observed spectra relate to the following functional groups:
890 cm-1 - RR'C = CH2,”bending vibrations”; 965 cm-1 – CHR = CHR1 “bending”
vibrations”; 1709 cm-1 - CO, “stretching vibrations”; 1166 cm-1 - C-O “stretching vibrations.”
Data on the composition of condensation products obtained by chromatography, and
combined gas chromatography and mass-spectrometry methods are shown in Table 4.
We concluded according to the results of the analysis that the greatest number of catalyst
deactivation compounds consist of isoprene oligomers. This suggests that the precursors of
coke formation are the components of the reaction mixture and hydrogenation products
thereof. Active catalyst sites are blocked in the course of catalyst performance.
Deposit formation can also cause a reduction in the diffusion rate of the reaction of
components mixture in the catalyst granules. All these changes can occur during the
hydrogenation reaction of acetylene compounds [22].
The first series of experiments using pure SC-CО2 for the regeneration of the catalyst was
conducted at temperatures of 343 K and 423 K, and pressures of 10, 20 and 30 MPa (Table
5), (Figure 5). A reduction of the initial weight of the catalyst (3.4 wt. %) is observed, which
corroborated the unique possibility to remove deposits through the ongoing review process. A
much greater effect can be obtained by increasing the mass of carbon dioxide used in the
process, changing the process parameters, and modification of the extractant agent (mainly by
the introduction of appropriate polar additives).
IR spectra of samples of regenerated catalyst (see Figure 6) confirm the presence of
important changes, particularly the reduction of the number of deactivated compounds.
Table 5. Operating conditions of the regeneration process
Run Extractant Temperature Pressure

(1) SC-СО2 343 K 10 MPa
(2) SC-СО2 343 K 20 MPa
(3) SC-СО2 343 K 30 MPa
(4) SC-СО2 423 K 10 MPa
(5) SC-СО2 423 K 20 MPa
(6) SC-СО2 423 K 30 MPa
(7) SC-СО2 + 3 wt. % methanol 343 K 15 MPa
(8) SC-СО2 + 3 wt. % methanol 343 K 20 MPa
Operating conditions are given in Table 5.
Figure 5. Variation of the mass of the catalyst in the regeneration process as a function of the mass of
extractant.
The area from 2500 cm-1 to 1500 cm-1gives the main information in the interpretation of
IR spectra. The analysis of this area pointed out unsaturated fragments in the compound
structure: C = C and C = O [23].
Figure 6. IR spectra of deactivated compounds of catalyst samples regenerated with pure and modified
SC-CO2. (1) - samples regenerated at P = 30 MPa and T = 423 K; (2) - samples regenerated at
P = 30 MPa and T = 423 K (3 wt. %, methanol); (3) - deactivated catalyst; (4) - fresh catalyst.
The presence of two C = C bonds (isoprene) in the conjugate state leads to the appearance
of absorption bands in the region of 1650-1600 cm-1, and an increase in their intensity.
Further accumulation of C = C bonds leads to several bands in this area, which sometimes
merge into a single broad band [24]. As shown in Figure 6, deactivated compounds with
absorption bands in the region of 1500 cm-1 are almost completely removed.
It can be considered, that the 1600 cm-1 and 1380 cm-1 absorption bands, correspond to
polar compounds or inorganic compounds, and that the low capacity of dissolving of pure
SC-СО2 prevents their removal.
The capacity to dissolve any polar substances by non-polar carbon dioxide can be
significantly increased by adding polar co-solvents to the fluid. Since the forces of interaction
between the molecules of a co-solvent and solutes are specific, there is often an increase in
the selectivity of the extraction method [9]. Supercritical CО2, without a co-solvent, weakly
dissolves polar compounds, while its power of dissolution increases significantly by the
addition a co-solvent [25-27].
The addition of 0.1 to 20 wt. %, of such modifiers as methanol, ethanol and others may
be performed before feeding the extraction solvent to the extractor [27]. The results of the
studies of the catalyst regeneration process using SC-CO2, modified by addition of 3 wt. %,
of methanol, are displayed in Figure 6. These data show that the regeneration efficiency
increases significantly with increasing temperature and pressure, but the most important
factor is the addition of methanol.
Figure 6, shows that the regeneration using modified carbon dioxide can remove polar
compounds more effectively compared to pure supercritical carbon dioxide, as shown by the
decrease in the intensity of the absorption bands 1600 cm-1 and 1400 cm-1. Thus, the SC-CO2
modified with a polar co-solvent can remove polar compounds from the coke.
Selection of optimal polar co-solvent, as well as its optimal concentration is required to

achieve the best result. On this basis, the influence of co-solvents of different nature on the
change of mass of catalyst was investigated (Figure 7).
Figure 7. Effect of different types of co-solvents on the variation of the mass of catalyst, at Т = 343 K
and Р = 20 MPa. (1) - chloroform; (2) - acetone; (3) - methanol; (4) – DMSO.
Figure 8. Changes in the mass of catalyst in the regeneration process as a function of the mass of CO2
with co-solvents. (1) - CO2 + DMSO; (2) - CO2 + Acetone: (3) - CO2 + Methanol; (4) - CO2 +
chloroform.
Chloroform, methanol, acetone and dimethyl sulfoxide (DMSO) have been selected for
this study. The concentration of co-solvent ranged from 0 to 9 wt. %.
The results of measurements of the variation of the mass of catalysts as a function of the
concentration of various co-solvents are displayed in Figure 7. The nature of these curves
shows that the variation of the mass of the catalyst increases with the rise of the concentration
of co-solvent, at first reaches a maximum, and then decreases thereafter. In almost all cases,
the optimum co-solvent concentration is about 7 wt. %.
The kinetics of the catalyst regeneration process using supercritical carbon dioxide
modified with optimal concentrations of polar additives (7 wt. %), and performed at
T = 423 K and P = 30 MPa, is presented in Figure 8.
As shown in Figure 8, the highest degree of extraction of deactivating compounds is
obtained using dimethyl sulfoxide as a co-solvent. This solvent has a higher polarity (4.05 D)
in comparison with other substances (chloroform: 1.14 D, methanol: 1.71 D, ethanol: 2.28 D,
acetone: 2.71 D) [28], that allows a more complete way of extraction of polar compounds.
5. COMPARISON OF THE CHARACTERISTICS OF THE NICKEL

ON KIESELGUHR CATALYST SAMPLES REGENERATED BY
CONVENTIONAL APPROACH AND SC-CO2 EXTRACTION
From the viewpoint of our studies, the most interesting and important work is that which
describes the regeneration of the deactivated catalyst containing nickel with thiophene, using
supercritical carbon dioxide [29]. The authors argue that the regeneration methods of catalyst
containing nickel by other approaches do not provide such benefits.
In particular, it is noticed that the recovery of the poisoned catalyst with hydrogen, at a
temperature of 473 K and a pressure of 2 MPa, for 20 hours, resulted in the recovery of only
13% of the initial catalyst activity. The regeneration of partially poisoned catalyst in similar
conditions has recovered 78% of its initial activity. The addition of 2-butyne during the
regeneration process did not significantly improved the results.
Thiophene is completely recovered into hydrogen sulfide (H2S), at higher reaction
temperatures (>473 K). This leads to the formation of nickel sulfide (Ni3S2) on the catalyst
surface, which is much more stable than the bulk compound sulfides [30].
Thus, various nickel catalyst regeneration processes have been studied, such as hydrogen
reduction, steam oxidation or a sequential oxidation treatment (0,005 to 25 vol. % in inert
gas) followed by hydrogen reduction. None of the processes studied has enabled the
restoration of the activity of the catalyst to the original initial state. Even with 90% of the
removal of sulfur from the catalyst, the full activity of the catalyst cannot be restored due to
effect of surface sintering.
Let us consider the measurement of the activity of the catalyst during the recovery of
2-butanone to 2-butanol, at a temperature of 373 K and a pressure of 1.7 MPa.
The regeneration process is implemented to eliminate the deactivating thiophene
compound, using supercritical carbon dioxide.
A method of continuous multistage extraction was carried out at 313 K, 41 MPa, with a
flow rate of 40 cm3 of CO2/h. The regeneration was stopped periodically, to take samples of
catalyst for testing the regenerated catalyst activity as a function of the extraction time.
The constant of the hydrogenation reaction rate was calculated assuming pseudo-first-
order kinetics with respect to 2-butanone. Typical results of 2-butanone conversion are
plotted as a function of time in Figure 9, for fresh and regenerated catalysts.
Figure 9. Pseudo-first-order kinetics of 2-butanone hydrogenation with 0.57 g of fresh catalyst

and 0.5 g of catalyst regenerated during 16 h.). (1) - fresh catalyst, kf = (1.05 ± 0.03) h-1g-1, R2 = 0.996;
(2) - regenerated catalyst, kf = (1.01 ± 0.02) h-1g-1, R2 = 0.999. (3) and (4) - corresponding to theoretical
approximations. (x is the speed of the hydrogenation reaction of 2-butanone).
Figure 10. Recovery ratio of the activity of the catalyst as a function of time.
The catalyst poisoned by thiophene displayed no hydrogenation activity. The conditions

of activation (2.1 MPa and 373 K) did not allow recovering catalyst activity, while the
supercritical CO2 extraction had a significant effect. The recovery ratio (RR) of the catalyst
activity was determined from the ratio of kr and kf, the pseudo-first-order rate constant of
regenerated and fresh catalysts, respectively. RR increased with regeneration time, as shown
in Figure 10.
Table 6. Activity of the samples of nickel on kieselguhr catalyst subjected to various

treatments in the hydrogenation of ethylene
Sample
Product Fresh Regenerated with SC- Regenerated with
Spent catalyst
catalyst СО2 + 3 wt. % СН3ОН pure SC-СО2
Ethane (in vol. %) 91.5 87.7 92.3 92.9
Ethylene (in vol. %) 8.5 12.3 7.7 7.1
After 16 hours, the ratio of recovery has reached a value, which is consistent to that of the
catalyst in its original level.
The results of this study confirm the high efficiency of the regeneration process using
supercritical carbon dioxide as compared to conventional regeneration methods. The use of a
supercritical fluid at low temperature also avoids the problem of catalyst sintering and the
reduction of the porosity.
The activity of a catalyst has been selected in our studies, as a criterion for the
hydrogenating ability of the catalyst, in the ethylene to ethane hydrogenation process, for the
pulsed supply of equimolecular ethylene-hydrogen mixture. The results obtained are
presented in Table 6.
The higher percentage of conversion of ethylene to ethane in the table shows that the
catalytic properties of the sample deactivated in the procedure are completely recovered after
treatment in a SC-CO2 medium (pure and modified with methanol).
Thus, the recovered nickel on kieselguhr catalyst activity demonstrates the effectiveness
of the use of supercritical fluid extraction process, in the regeneration studies of carburized
catalyst and the recovery of various organic substances from the solid medium.
The use of supercritical fluid media, such as supercritical carbon dioxide, was justified in
doing so, which is an effective solution to the problem of energy and resource conservation in
industry.
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of Analytical Mass Spectrometry and Chromatography, 2014, 2: 1-14.
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Sagdeev, A. A., Yarullin, R. S., Yakushev, I. A. The Synthesis and Regeneration of
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Catalyst “Nickel on Kieselguhr” Using Supercritical Carbon Dioxide. Supercritical
fluids. Theory and practice. 2010, 5, 1: 40-51.
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Catalyst of Selective Acetylene Hydrogeation by the Supercritical CO2. Supercritical
fluids: theory and practice. 2006, 1, 2: 5-12.
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[16] José, T. C. Compressed Gases as Solvents. Nedra publisher, Moscow, 1981: p. 161.
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University of Wisconsin, 1981.
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Liquids of Low Volatility in Supercritical Carbon Dioxide. J. Phys. Chem. Ref. Data,
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Amirhanov, D. G., Maksudov, P. N. Prospects for the Use of Sub- and Supercritical
Extractant for the Extraction of Metals from Bitumen and High Oil, Butlerov
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Supercritical Fluid Extraction Process in the Regeneration of the Catalyst “nickel on
kieselguhr,” Bulletin of the Kazan Technical University. Tupolev A. N., 2010, 2: 27-32.
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Organic Synthesis. Guide for Chemical and Biological Specialty of Teacher Training
Institutions, 1979: p. 256.
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[23] Vasil'ev, A. V., Grinenko, E. V., Shchukin, A. O., Fedulina, T. G. Infrared
Spectroscopy of Organic and Natural Compounds. Saint-Petersburg State Forest
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University Publisher, Gorno-Altaisk, 2009: p. 95.
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Chapter 3
REGENERATION OF THE ACTIVE ALUMINA

CATALYST USED IN THE METHYL PHENYL
CARBINOL DEHYDRATION PROCESS BY
SUPERCRITICAL CO2 EXTRACTION
A. T. Galimova1, A. A. Sagdeev1, F. M. Gumerov2,*

and N. N. Sarimov1
1
Nizhnekamsk Institute for Chemical Technology, Nizhnekamsk, Russia
2
Kazan State Technological University, Kazan, Russia
ABSTRACT
The nature of deactivating deposits form on the active alumnia catalyst in the methyl
phenyl carbinol dehydration process is analyzed. Solubility of one of them: styrene, was
measured in supercritical carbon dioxide in the temperature range from 323 to 333 K and
the pressure range from 12 to 24 MPa. Results have been described with using the Peng-
Robinson equation of state. The possibility of regeneration of the catalyst using pure
supercritical carbon dioxide, and supercritical carbon dioxide modified with polar
additive is investigated at 423 K, in the pressure range 10-30 MPa. The kinetic of
regeneration of the catalyst with SC-CO2 was studied. A comparison of activities of
freshly prepared, traditionally regenerated, and regenerated with SC-CO2 catalyst
samples, showed that the proposed method is very competitive compared with the
conventional regeneration techniques.
Keywords: active alumina catalyst, catalyst regeneration, catalyst activity, methyl phenyl
carbinol, styrene, supercritical carbon dioxide, solubility, Peng-Robinson equation of
state
*
46 A. T. Galimova, A. A. Sagdeev, F. M. Gumerov et al.
1. INTRODUCTION
Processes for the joint preparation of styrene monomer (“SM”) and propylene oxide
(“PO”) are known in the art and are commonly referred to as “SM/PO” processes. An SM/PO
process is for example described in WO 00/05186. In general, an SM/PO process comprises
the steps of:
a) reacting ethene and benzene to form ethylbenzene,

b) reacting ethylbenzene with oxygen containing gas to form ethylbenzene
hydroperoxide,
c) reacting ethylbenzene hydroperoxide with propene in the presence of an epoxidation
catalyst to form propylene oxide and 1-phenylethanol, and
d) dehydrating 1-phenylethanol into styrene in the presence of a suitable dehydration
catalyst.
During said steps (b) and (c), methyl phenyl ketone is formed as a side-product. Prior to
said step (d), this methyl phenyl ketone may be converted with hydrogen to methyl phenyl
carbinol (1-phenylethanol).
During said step (b) of oxidising ethylbenzene into ethylbenzene hydroperoxide, not all
ethylbenzene reacts. Said unreacted ethylbenzene may be recycled to the oxidation reactor.
The oxidation reaction is carried out at a concentration below 20 wt.% of ethylbenzene
hydroperoxide on the basis of the total weight of the reaction mixture. In general, at or above
this concentration, the production of the side-products methyl phenyl carbinol and methyl
phenyl ketone grows relative to the amount of ethylbenzene hydroperoxide, causing
inefficient loss of reactant ethylbenzene.
Hence, the concentration of ethylbenzene hydroperoxide in the reaction mixture is kept
relatively low. There is a continuing desire among those skilled in the art to achieve a high
oxidation rate when working under the above maximum ethylbenzene hydroperoxide.
The first plants using this technology appeared in the 1970s; in Russia, the SM/PO
process was employed at the industrial combine (now OAO) Nizhnekamskneftekhim, in
operation since 1982.
In domestic technology, the vapor phase dehydration of MPC is performed in the
presence of active alumina (mainly -Al2O3), in an adiabatic reactor with a fix bed catalyst.
The operating temperatures of the process are 520-590 K. To reduce the partial pressure of
hydrocarbons and to compensate for the endothermic effect of the target reaction, excess
water up to 10 mol/mol MPC is used. At intervals of about once a month, the oxidative
regeneration of the catalyst is performed (steam + air à T > 770 K).
At present the service life of TU 6-68-146-02 AOK 63-22K dehydration alumina catalyst
(OAO Katalizator, Novosibirsk, Russia) with a phase composition  +  alumina, with
limitable impurities up to 0.1 wt. % Na2O, 0.05 wt. % Fe(III) is one year, due to exclusivity to
the decrease of the specific activity of the catalyst.
Active alumina catalyst is typically used in the methyl phenyl carbinol (MPC) styrene
catalytic dehydration process. Activated alumina is manufactured from aluminium hydroxide
by dehydroxylation to produce a highly porous material. This material can have a surface area
significantly over 300 m2/g.
Regeneration of the Active Alumina Catalyst … 47
Alumina in the methyl phenyl carbinol (MPC) styrene process, of catalytic dehydration,
deactivate over time. There are several mechanisms for deactivation: steaming or heat and
water vapor cause surface area degradation, agglomeration of adsorbent, coke formation due
to the reactive species.
Fairly detailed studies of the methods for reactivating catalysts to return to the
dehydration process have shown that the catalysts can be reactivated to an activity
comparable to that of the initial catalyst.
To determine the nature of the pollutants on the surface of the catalyst, a series of tests
were conducted; they include analyses by chromatography, thermogravimetry and infrared
spectroscopy. The main pollutants on the spent active alumina catalyst were found to be
styrene oligomers, methyl phenyl carbinol esters, styrene polymer and resins.
The solubility of deposits on the catalyst surface was investigated. The measurement of
the solubility of styrene and the major components of pollutants in supercritical carbon
dioxide was preceded by the study of the dependence of the concentration of the substance in
carbon dioxide, the degree of filling of the test substance in the extraction cell.
The regeneration of the active alumina catalyst was carried out at 423.15 K, in the
pressure range from 10 to 30 MPa, using pure supercritical carbon dioxide and supercritical
carbon dioxide with polar co-solvents such as chloroform, methanol, acetone and dimethyl
sulfoxide (DMSO). The loss of weight of catalyst samples during each extraction was
determined.
Experiments have shown that the efficiency of regeneration was increased by 120%, by
the addition of DMSO, which allowed the elimination of polar compounds, thereby reducing
the amount of coke deposits.
The results of studies of the regeneration process of the active alumina catalyst, in
supercritical carbon dioxide media, show a successful regeneration by this method, using
supercritical carbon dioxide with polar dimethyl sulfoxide (DMSO).
2. METHYL PHENYL CARBINOL DEHYDRATION PROCESS;

SPENT CATALYST CHARACTERISTICS AND DESCRIPTION OF
THE CONVENTIONAL REGENERATION PROCESS THEREOF
Active alumina catalyst is used in the methyl phenyl carbinol (MPC) styrene catalytic
dehydration process. This process is carried out at a temperature from 523 to 593 K,
according to the reaction [1]:
С6Н5 СНОН - СН3  С6Н5  СН = СН2 + Н2О (44  8 kJ/mol),
The physico-chemical characteristics of the catalyst are listed in Table 1 [2]. As methyl
phenyl carbinol dehydration reaction takes place, a coke deposition on the surface of the
catalyst will follows, which reduces its activity [3]. Usually, after running for 400 to 600
hours, the catalyst is subjected to regeneration, in order to recover its activity. Catalyst
regeneration is carried out with a steam-air mixture at a temperature from 673 to 873 K.
However, this method does not achieve the regeneration of the catalyst to the full extent,
since it is impossible to remove all coke, some of it will inevitably remains on the catalyst
surface. There is also a risk of sintering of the catalyst due to the formation of a styrene
polymer, which naturally leads to a reduction of the life of the catalyst [4].
In order to investigate the possibility of regenerating the activated alumina catalyst using
supercritical fluid media, the following tests were conducted in order to know the nature of
the pollutants on the surface of the catalyst, namely: chromatographic, thermogravimetric and
infrared spectroscopic analyses.
Composition of the spent catalyst sample was determined by gas-liquid chromatography
[5], using the chromatograph “Chromatec-Crystal 2000” with a flame ionization detector on
the capillary column CP-WAX52. The analysis is performed using analytical columns of
50 m in length, and a diameter of 0.32 mm, (the thickness of the fixed bed of polyethylene
glycol is 1.2 m) at a temperature of 363 K. Nitrogen is used as carrier gas. An amount of
liquid sample of 0.6 mm3 was introduced into the evaporator; the temperature of the
evaporator was set in the range of 283 to 473 K; the temperature of the detector was 533 K.
The analysis of chromatogram was carried out using the Net Chom v1.5 software.
The composition of the extract of catalyst provided by the chromatographic analysis is
given in Table 2 [6].
The nature and the amount of coke deposited on the surface of the deactivated catalyst
were determined by the integrated method of thermal analysis, in other words, simultaneously
by thermogravimetry and derivative thermogravimetry (TGA-DTG) [7], using a “F.PAULIK”
derivatograph system, in the temperature range from 293 to 1123 K, in dish-shaped platinum
crucibles, heated in the open air, with a sample mass of 0.6 g. The absolute error in the
temperature measurement is ± 4 K, and the relative error in the determination of the mass is
equal to ±0.5% [8].
Table 1. Physico-chemical characteristics of catalyst
Characteristics Active alumina АОА-1

White cylindrical granules; creamy shade is
1. Appearance
considered acceptable
2. Granule size:
diameter: 5.0 ± 1.0 mm,
length:, less than 18 mm
3. Lose weight density 450-550, kg/m3
4. Abrasion strength, more than 65.0%
5. Specific surface, more than 200 m2/g
Table 2. Spent active alumina catalyst composition
Name Catalyst content, wt. %

styrene 19.63
methylstyrene 16.44
acetophenone 6.54
methyl phenyl carbinol 28.22
phenol 16.89
others 12.28
TGA- DTG data are shown in Figure 1, and Table 3. Heating the coked catalyst sample
leads to progressive reduction of its mass accompanied by one endothermic and two
exothermic effects, as clearly shown in the DTA curve. Endothermic effects (373-393 K) are
probably due to the loss of weakly water bound and low boiling hydrocarbons. Exothermic
effects (maxima at 593 K and 763 K) result of the onset of the oxidation process.
Endothermic effects (833-1123 K) indicates the presence of coke deposits on the catalyst
surface. The presence of these two effects suggests heterogeneity of the deposits. The
maximum mass loss of deactivated catalyst is observed at temperatures from 713 to 833 K.
The total amount of coke deposits Δm reached 9.7%.
The analyses of IR spectra of fresh and deactivated catalyst (Figure 2) have shown that
the deposits are composed of reaction products. There are styrene oligomers, MPС esters,
styrene polymer and resins.
The deactivated catalyst is dispersed in chloroform, to carry out the infrared
spectroscopic analysis [9]. After two hours, the extract is spread on the surface of a plate
coated with NaCl; the chloroform is then evaporated resulting in the formation of a thin film
of the test compound. The plate is placed in the FTIR spectrophotometer Vector 34, and the
spectrum in the wavelength range of 400 to 2000 cm–1 is recorded [8].
Figure 1. TG-DTG curves of the deactivated active alumina catalyst: (1) - temperature variation with
time, (2) - DTG curve, (3) - TG curve.
Table 3. Data of the joint analysis of deactivated catalyst:

IR spectroscopy and TGA-DTG
Temperature, K Name Catalyst content, wt. %

1 <393 Volatile components 1.9
2 673-713 Styrene polymer 1.6
3 713-833 Resins 4.8
4 833-1123 Coke 1.4
Figure 2. IR spectrum of fresh and deactivated active alumina catalyst: (1) - fresh catalyst; (2) -
deactivated catalyst; (A) - MPC esters, (B) - polystyrene oligomers, (C) - polystyrene polymers.

The solubility of deactivated compounds of the catalyst has been studied in connection
with the exploration of the potential for active alumina SCFE regeneration. An experimental
facility was created for this purpose (Figure 3).
The installation consists of a high pressure fluid pump (LIQUPUMP 312/1), which
provided a fixed flow rate of solvent within 0.05 to 8.99 cm3/min, and the outlet pressure up
to 30 MPa. Flow rate is set on the control panel of the pump with an accuracy of
0.01 cm3/ min; the pressure system is controlled by two separate pressure gauges (at the pump
outlet and directly in the cell).
By circulating through the cooling jacket of the pump and the low temperature annular of
the heat exchanger, the refrigerant ensures the proper functioning of the pump and cooled
carbon dioxide at a temperature of 258 K, which is measured by a chromel-copel
thermocouple located in the low temperature heat exchanger.
The extraction cell is placed in a constant temperature bath, thereby maintaining the
experiment at a constant temperature. In addition to the thermostat installed inside the
constant temperature bath, the temperature in the constant temperature bath is controlled by a
mercury thermometer.
In the experiments two types of extraction cells were used. A cell having a volume of
370 cm3 was used for the study of the solubility of styrene and a cell with a volume of 120
cm3 to investigate the solubility of other substances. There is a throttle device installed
upstream of the sample collector, via which the pressure of the supercritical solution is
reduced to atmospheric pressure. Downstream gas flow rate of the extract collector is
measured with a gas flowmeter. The determination of solubility was carried out by the
dynamic method [10]. Before supplying the solvent, the encapsulated cell filled with the test
substance was incubated for 20 minutes. The solvent supplied into the extraction cell is
preheated with a heating coil in order to minimize temperature gradients.
Figure 3. Diagram of the experimental setup: (1) - bottle of carbon dioxide; (2) - low temperature heat
exchanger; (3) - fluid pump; (4) - constant temperature bath; (5) - heater; (6) - extraction cell; (7) -
throttling device; (8) - extract collector; (9) - gas flowmeter; (a) - direct refrigerant; (b) - reverse
refrigerant; (PI) - pressure control.
The studies of the solubility of pure liquids in SC-CO2 include the following steps:
 Loading the test substance into the cell;

 Supply of solvent;
 Measurement of the volume of the solvent and the mass of solute.
 Determining the mass of a substance dissolved in supercritical fluid solvent, which is
carried out by weighing the extract collected before and after the experiment.
To eliminate the influence of errors associated with the concentration of the supercritical
solution out of equilibrium, experiments were performed to investigate the dependence of the
concentration of the test substance in SC-CO2, on the flow rate of supercritical fluid solvent
and the filling level of the extraction cell. Let us consider the effect of the solvent flow rate
and the filling of the cell volume, for example on a sample of styrene [11]. Figure 4, shows a
diagram of the dependence of styrene concentration in the supercritical solution relative to the
solvent flow rate.
As shown in Figure 4, the concentration of a substance in solution is reduced (non-
equilibrium concentration in zone II) with increasing solvent flow, starting from a certain
value. The solvent flow rate in the main experiments was selected from values corresponding
to zone I, in order to obtain reliable results that match the concept of “solubility.”
An important factor in obtaining reliable data on the solubility is the level of filling of the
cell with the test substance. Observations of the phase equilibrium in the “styrene - carbon
dioxide” system, using optical cell clearly show that, according to certain levels of ultra-
boundary styrene filling, above the optimum; the dissolution of carbon dioxide in the liquid
phase during the injection of CO2, is followed by the increase in volume of the liquid phase
and movement of the phase boundary to the upper boundary of the measuring volume.
Figure 4. Variation of the concentration of styrene in SC-CO2 as a function of SC-CO2 flow rate,
at T = 323.15 K and P = 12 MPa: (I) - equilibrium concentration zone, (II) - unsaturated region of
supercritical carbon dioxide.
Typically, this means that the marked boundary is outside the working volume (in the
upper outlet tube) and injecting an additional amount of carbon dioxide, operates as a piston
and moves the liquid phase in the separator, which distorts the base of the method of
solubility measurement.
For this reason, the method for measuring the solubility of styrene and the major
components of pollutants in supercritical CO2 was preceded by the study of the dependence of
the concentration of the substance in carbon dioxide, the degree of filling of the test substance
in the extraction cell. The invariability of concentration value (zone II), corresponding to a
certain range of the filling level, is the basis thereof, to take the equilibrium concentration or
the desired solubility. Figure 5 to Figure 10, illustrate the dependence of the styrene
concentration in supercritical solution on the cell filling volume.
An experimental setup was built in order to regenerate the active alumina.
The modification of the extraction process can be carried out by adding co-solvent in
carbon dioxide prior to introduction into the cell.
An experimental unit (Figure 11) was designed to be able to use an extraction fluid, both
pure and modified; it is protected by a patent of the Russian Federation [12].
The device is mounted on the base of the “LIQUPUMP 312/1” fluid piston pump. The
supply of the liquid carbon dioxide in the suction circuit must be provided during the normal
operation of the pump. Liquefaction takes place in the condenser and directly in the pump, by
the flow of refrigerant in the pump cooling jacket and in the annular of the condenser. The
pump design feature is the presence of two pump heads, pistons which smooth the pulsation
of the unsteady fluid flow. This allows to achieve a high degree of SCF feed uniformity. SFE-
400 high-pressure syringe pump is used to drive the modifier in the vessel. The required
concentration of modifier in supercritical CO2 (1 to 9%) is adjusted by controlling the co-
solvent flow rate in the range of 0.01 to 11 cm3/min. Check valves used in the system prevent
the return of gas and liquid to the pump.
Figure 5. Variation of the styrene concentration in SC-CO2 as a function of the level of solute in the
extraction cell, at a temperature of 323 K and a pressure of 20 MPa: (I) - zone of unsaturated
supercritical carbon dioxide, (II) - zone of equilibrium concentration, (III) - zone of stripping droplets
[11].
[11].
[11].
[11].
[11].
[11].
Figure 11. Experimental diagram of the setup: (1) - СО2 bottle; (2) - feed fluid pump with СО2; (3) -
refrigeration unit; (4) - condenser; (5) - feed syringe of co-solvent; (6) - co-solvent vessel; (7) -
extraction cell; (8) - heat exchanger; (9) - tubular electric heaters; (10) - regulating valve (with throttle
device functions); (11) - extract collector.
The extraction cell is placed in a heat exchanger built with a thick wall copper tube.
Heating is provided by the heating coil, wound around the heat exchanger. The temperature of
the extraction cell is fixed at a set point, by means of an electronic controller 2TRM1.
Chromel-copel thermocouples mounted on the ends of the cell are used to control the
temperature. The accuracy of temperature measurement is estimated to be within ± 0.05 K.
The catalyst was weighed before and after the experiment, using a “SARTOVLT-150-P”
electronic balance with an accuracy of ± 10–6 kg, to determine the variation of the mass of the
catalyst, and thus, the extent of deactivated extracted substances.
An amount of spent catalyst required for the experiment was loaded into a beaker of
known mass, to investigate the regeneration of the catalyst of active alumina. The extraction
cell, with the beaker installed therein, is then inserted into the heat exchanger. CO2 passes
from the bottle through a fine filter and a condenser and enters the high pressure pump, where
it is compressed to the desired pressure. The co-solvent is then fed through a three-way valve
to the common line, via a syringe pump.
The modified supercritical CO2 enters the heat exchanger, reaches the temperature T > Tc
and moves to the extraction cell. The substances dissolved in the modified SC-CO2 pass
through the throttle valve, wherein the pressure reduction occurs, and then entered in the
extraction collector. The temperature of the process is kept constant with an electric heater,
inside the capillary tube, between the extraction cell and the control valve, which prevents the
premature release of substances dissolved in the SCF.
Preliminary studies were carried out to measure the effect of the mass flow rate of
supercritical CO2, on the change of mass of spent catalyst, and then the flow rate was set in
the experiments, to ensure a high level of saturation of the supercritical solvent. From these
experimental results, a dependency graph, of the variation of mass of active aluminum oxide,
in the flow of supercritical solvent was drawn (Figure 12). The optimum flow rate value
needed to maintain a high degree of saturation of the supercritical solvent (zone I) is selected
in accordance with this diagram.
Figure 12. Variation of the mass of active alumina catalyst as a function of the SC-CO2 mass flow
(T = 423 K and P = 20 MPa).
Figure 13. Test apparatus for MPC vapor-phase dehydration process: (1) - reactor, (2) - evaporator, (3) -
separator, (4) - reflux condenser, (5) - collector of hydrocarbon distillate fraction, (6) - collector of
aqueous distillate fraction, (7) - MPC feed metering pump, (8) - water feed metering pump, (9) - MPC
supply vessel, (10) - water supply vessel.
Moreover, the conversion and the selectivity of the regenerated catalyst were measured in
the experimental apparatus shown in Figure 13 [3]. The methyl phenyl carbinol (MPC)
fraction is fed from the vessel (9), by the pump (7), in the evaporator (2) filled with broken
quartz glass. Distilled water is also supplied in the tank (10), by the pump (8), where
evaporation thereof, at a temperature of 573 K occurs.
The steam and MPC vapors are supplied from the evaporator into the reactor filled with
catalyst (1), wherein the hydration reaction goes on. The products of reaction move from the
bottom of the reactor to the reflux condenser (4), wherein the dehydration reaction proceeds.
The condensate then flows into the separator (3), where it is separated into aqueous and
hydrocarbon fractions. The hydrocarbon phase (upper layer) moves from the separator into
the receiver (5), and the aqueous phase (bottom layer) flows into the receiver (6). The catalyst
in the vessel (5) is then analyzed by chromatography. The experimental conditions were as
follows: the mass ratio of MPC/Н2О = 1, MPC and Н2О streams are 45 cm3/h, the volume of
the catalyst loaded into the reactor is 100 cm3. The duration of the dehydration process of the
MPC vapor phase is 10 hours.
4. SOLUBILITY OF CATALYST DEACTIVATION

COMPOUNDS IN SC-CO2
It is necessary to investigate the solubility of pure components in supercritical carbon
dioxide for performing supercritical fluid extraction, in order to regenerate the active alumina
catalyst. The results of the solubility measurements of styrene, acetophenone and methyl
phenyl carbinol are shown in Table 4 [13, 14]. The accuracy of the solubility measurements
of styrene, methyl phenyl carbinol and acetophenone varies from 6.9 to 12%.
An equation reported in [15] was used to describe the solubility of substances in
supercritical CO2:
 ln y k Vmk 1  ln  k
  
P RT P P , (1)
k
where yk is the mole fraction of solute k in the supercritical solvent, Vm is the molar volume,
P is the pressure and k is the volatility coefficient.
The integration of equation (1) in the range of P0 to P, gives:
ln yk  ln y0k 
Vmk
P  P0   ln P  ln k0
RT P0 k , (2)
where y k  y k ( P0 ) and
0
k0  k ( P0 ) . In many works, the parameter P0 was neglected,
leading to additional errors. In this regard, the equation for determining the coefficient of
volatility ln k was solved, taking into account P0, to minimize the mean square error.
Table 4. Results of the solubility (у) of styrene, acetophenone and methyl phenyl
carbinol, at different temperatures and pressures
Styrene
Т = 323 К Т = 328 К Т = 333 К
Р, MPa у, mole fraction Р, MPa у, mole fraction Р, MPa у, mole fraction
12 0.0109 12 0.0115 12 0.0150
15 0.0135 15 0.0125 14 0.0150
18 0.0267 18 0.0256 15 0.0156
20 0.04383 20 0.0438 18 0.0267
22 0.05760 22 0.061789 20 0.0443
24 0.0557 24 0.0623 24 0.0664
Methyl phenyl carbinol
Т = 320 К Т = 325 К Т = 330 К
12 0.0172 12 0.0072 12 0.0014
15 0.0205 15 0.0125 15 0.0079
18 0.0293 18 0.0265 18 0.0225
20 0.0386 20 0.0433 20 0.0531
22 0.0497 22 0.0652 22 0.0803
24 0.0600 24 0.0803 24 0.0943
26 0.0684 26 0.0979 26 0.1205
Acetophenone
Т = 320 К Т = 325 К Т = 330 К
12 0.0814 12 0.0842 12 0.0871
15 0.0851 15 0.0884 15 0.0900
18 0.0893 18 0.0941 18 0.1004
20 0.0950 20 0.1043 20 0.1161
22 0.1011 22 0.1174 22 0.1236
24 0.1093 24 0.1200 24 0.1263
26 0.1151 26 0.1271 26 0.1302
The coefficient of volatility of the k component at T and V = const., reads according to

[16]:
  n  Z    dV
ln k      1 M  ln Z
VM  nk T ,V  VM , (3)
n   nk
where k is a total number of moles, nk is a number of moles of component k, VM =
V/n is the molar volume, Z is the compressibility factor calculated by the equation of state.
The compressibility factor was determined according to the Peng-Robinson equation of
state:
RT a
P  2
VM  b VM  2bVM  b 2 , and (4)
PV M
Z
RT (5)
The parameters a and b of Equation (4) are defined by the following relations:
i , j
 b 
a    i , j ai , j   yi y j
b 
i, j  i, j  , (6)
b    i , j bi , j yi y j
i, j
, (7)
The coefficients ai,j = aj,I and bi,j = bj,I depend on the critical temperature Тc and critical
pressure Рc of the mixture components; i,j = j,i, i,i = 1, γi,j = γj,i, γi,i = 1, βi,j = βj,i, βi,i = 1 are
binary interaction parameters and xi = ni/n is the mole fraction of the component i in the
mixture.
In literature sources, different numbers of binary interaction parameters are used, not only
one adjustable parameter βi,j, but several parameters like i,j, βi,j or, i,j, γi,j. In our case, there
are three adjustable parameters, namely βi,j, i,j and γi,j [17, 18].
We have introduced the following notation:
b  b  n    i , j bi , j ni n j
i, j
, (8)
i , j
 b 
a  a  n    i , j ai , j 
2  ni n j
b 
i, j  i, j  (9)
nz
The derivative
nk was calculated by integrating (3). For this purpose, we multiply the
nVM
equation (4) by RT , and taking into consideration the compressibility factor (Equation 5),
we obtain:
nz   nVM 1 anVM 

    
nk nk  M
V  b RT V 2
M  2bVM  b 2 

 

V

1 V a n2  
 V
   n
 
1 a 

2 
nk  V  b  n RT V 2
 2b V  b 2
n 2 
 n k  
V  b RT V 2
 2b V  b 
 1 n b 1 1 a 2 a V  b  b 
V    
 V  b V  b  k
2
n RT V 2
 2b V  b 2
n k RT V  2b V  b 2
2
 
2
nk 
 1  n 2 a V  b   b 1 1 a 
V     
V  b  V  b 
2

RT V 2  2b V  b 2 2  nk RT V  2b V  b nk 

2 2

VM  V 2 aVM  b VM  b 1 VM a
  M
  

VM  b  VM  b 2 RT VM2  2bVM  b 2 2  nk RTn VM2  2bVM  b 2 nk
 (10)
Substituting (10) in (3), we have:
  
dVM b dVM 2a b VM  b
ln  k  b    V   V dVM 
V VM  b  n k
Vm M Vm M  b
2
RT n k Vm
2
M  2bVM  b 2  2

1 a dVM

RTn n k VM
V 2
M  2bV  b 2
 ln Z
(11)
Let us consider each integral separately under the assumption that VM > b:


dV 1  V  1  V  1  b 
V VM VMM b   b ln VM M b   b ln VM M b    b ln1  VM 

M VM
(12)
 
dV 1 1
V VM Mb2  VM  b  VM  b
M V M
(13)

VM  b 1 VM

1 
 V  1 2 b   
 V
Vm
2
 2bVM  b 2 
2
dVM 
2b VM2  2bVM  b 2
 ln  M

 
4 2b 2  VM  1  2 b  V 
M VM
M

1 VM

1  V  1 2 b 
ln  M 
 
2b VM  2bVM  b
2 2
4 2b  VM  1  2 b 
2
  (14)
   


dV 1  V  1 2 b  1  V  1 2 b 
V VM2  2bVMM  b 2   2 2b ln VM  1  2 b    2 2b ln VM  1  2 b 
   
 M  VM  M 
M
(15)
Let us substitute (12) - (15) in (11):

 b  b 1 a b VM
ln  k   ln 1     
 nk VM  b RTb nk VM  2bVM  b
2 2
 VM

a 
b  VM  1  2 b 

1  a  VM  1  2 b  
 ln Z 
ln 
  ln

2 2 RTb nk  VM  1  2 b  2 2 RTbn nk  VM  1  2 b 
2  
b b  1 a VM 
  ln 1     
2 
VM nk  M
V  b RTb V 2
M  2bV M  b 

1  1 a a b
   ln 

  VM  1  2 b  
  ln Z
2 2 RTb  n nk b nk   
  VM  1  2 b  (16)
Let us transform in (16) the parentheses in the add end:
1 a VM 1 VM a VM
   
VM  b RTb VM  2bVM  b
2 2
b VM  b RTb VM  2bVM  b 2
2
1 1 VM 1 V 1 aVM 
    M   1
2 
VM  b b VM  b b  VM  b RT VM  2bVM  b 
2
Using (4) and (5), we have:
1 a VM Z
  1
VM  b RTb VM  2bVM  b
2 2
b (17)
Let us introduce the following notation:
aP bP
A ,B
RT 2
RT . (18)
Then the equation (16) with (5), (17), and (18) can be rewritten as:
 B  b  Z  a  1 a 1 b 
ln  k   ln 1      1     
 Z  nk  b  2 2 RTb  na nk b nk 
 ln 

 Z  1 2 B  
  ln Z   ln Z  B 
1 b
Z  1 
 
 Z  1 2 B   b nk

A  1 a 1 b
   ln 

  Z  1 2 B 


2 2 B  na nk b nk   
  Z  1 2 B   (19)
We write out expressions for the derivatives:
b 1 1
nk

nk
j
b
k, j k, j nj 
yk
 j
k, j k, jb уj
(20)
k , j
a  b  b  i , j ai , j
 2  k , j a k , j   
 i , j 1
b 
nj  i , j
 i, j b ni n j 
nk j  k, j  nk i, j bi , j
k , j
 b  b  1 b   i , j ai , j
 2  k , j a k , j    1 i , j  i , j b i , j ni n j 
 1
n j  
b  n  b nk
j  k, j   i, j i, j
b
k , j i , j
 b   1 b   b 
 2n   k , j a k , j   y j  n  1 i , j ai , j  i , j   yi y
b  b 
j  k, j   b nk  i, j  i, j  (21)
By introducing the following notation:
k , j
2  b 
Ak    k , j ak , j   yj
a j b 
 k, j  , (22)
1 b 1
Bk  
b nk b yk
 j
b
k, j k, j yj
(23)
i , j
 b 
Ck  Bk  1  i , j ai , j  i , j 
1  yi y j
a b 
i, j  i, j  , (24)
we obtain the final expression for the coefficient of volatility:
 Ak  Ck  Bk ln Z  1  
 2 B
ln  k  Bk Z  1  ln Z  B  
A

2 2B 
 Z  1 2 B  ,  (25)
Where the compressibility factor Z is defined from the equations (4) and (5):
Z 3  (1  B)Z 2  ( A  3B 2  2B)Z  ( AB  B 3  B 2 )  0 (26)
According to the choice of the number of the adjustable coefficients i,j, βi,j and γi,j, the
following mixing rules are obtained [15].
1, i  j
If i,j = 1 i,j and  i , j   , then the mixing rules are as follows:
0, i  j
i , j
 b 
a   ai , j   yi y j , b   bi ,i yi
b 
i, j  i, j  i
(27)
1, i  j
 i, j  
If 0, i  j , then:
i , j
 b 
a    i , j ai , j   yi y j , b   bi ,i yi
b 
i, j  i, j  i
(28)
If βi,j = 0 i,j, then the following mixing rule is credible:
a   i , j ai , j yi y j , b   i , j bi , j yi y j
i, j i, j (29)
The calculation of the adjustable binary interaction parameters introduced in these mixing
rules was done in taking into account the best mean square approximation with the
experimental results.
Let us assume that the experimental results obtained at a constant temperature and
variable pressure are yk  yk ( ps ), s  0,, n , then the binary interaction parameters i,j,
s
βi,j, γi,j are determined on this basis [19]:
2
1 n  y ks  y k ( Ps ) 
  min   y s 
n s 0 
 , , 
k  , (30)
s
where yk(Ps) is calculated by substituting the corresponding values of Ps and y k in the right-
hand member of the expression (2).
However, it is difficult to estimate the properties of the functional (30), and it is
impossible to use specific gradient or relaxation methods thereof for minimizing, because the
step scan access method was used to calculate the binary interaction parameters.
With the determination of the i,j, βi,j, γi,j parameters, the equation (2) can be regarded as
an approximation to the solubility function, which depends on the pressure at constant
temperature. It can be seen from this equation that there exits more than one solution y k at a
pressure P , as was confirmed by numerical experimental results. Here, the equation (2) was
used only to clarify the parameters of a linear piecewise interpolation, of the experimental
results in a predetermined pressure range.
Table 5 shows the binary interaction parameters and mean square error calculated by
the formula (30). It is obvious that the use of three binary interaction parameters give the
smallest mean square error.
Table 5. Numerical experiments results
σi,j βi,j γi,j Δ Equation

Т = 323 K
1.08751 1.8751 0.0000 0.0748 (6), (7)
0.7876 – 0.0342 0.1017 (29)
1.0000 1.8483 – 0.1408 (27)
Т = 328 K
1.0758 1.6098 0.0000 0.0717 (6), (7)
0.7798 – 0.0330 0.0937 (29)
1.0000 1.7616 – 0.1249 (27)
Т = 333 K
0.9909 2.5289 0.0000 0.1048 (6), (7)
0.7266 0.0000 0.0541 0.1228 (29)
1.0000 1.5092 0.0000 0.1566 (27)
Figure 14 to Figure 16, show the dependence of the solubility of styrene in supercritical
carbon dioxide along the isotherms 323 K, 328 K, 333 K. The results obtained for the
determination of solubility, confirm that the use of the Peng–Robinson equation at these
temperatures, in the pressure range from 8 to 24 MPa, causes experimental errors of the order
of 15.8%.
Figure 14. Results of the solubility of styrene in SC-CO2 at 323K: (1) - experimental data; (2) - curve
calculated using three binary interaction parameters (σi,j, βi,j, γi,j); (3) - curve calculated using two
adjustable parameters (γi,j, σi,j); (4) - curve calculated using a single adjustable parameter (βi,j).
Figure 15. Results of the solubility of styrene in SC-CO2 at 328 K: (1) - experimental data; (2) - curve
Figure 16. Results of the solubility of styrene in SC-CO2 at 333K: (1) - experimental data; (2) - curve
Significant differences between the experimental results on the solubility of styrene in

supercritical carbon dioxide, obtained in several studies, were observed. The factors behind
these differences could be the tendency of polymerization of styrene and the presence of
polymer phase, differences in the nature of polymerization inhibitors, the high volatility of
styrene impurities, and the deviations between the equilibrium concentrations of styrene in
supercritical carbon dioxide [20].
Lines are description according to the Peng-Robinson equation of state with three adjustable
parameters.
Figure 17. Variation of the solubility of styrene in SC-CO2, at T = 323 K, T = 328 K and T = 333 K, as
a function of pressure.
parameters.
Figure 18. Variation of the solubility of methyl phenyl carbinol in SC-CO2, at T = 320 K, T = 325 K
and T = 330 K, as a function of pressure.
parameters.
Figure 19. Variation of the solubility of acetophenone in SC-CO2, at T = 320 K, T = 325 K and
T = 330 K, as a function of pressure.
Table 6. Numerical experiments results
Styrene
Т = 323 К Т = 328 K Т = 333 К
σi,j 1.0875 σi,j 1.0758 σi,j 0.9909
βi,j 1.8751 βi,j 1.6098 βi,j 2.5289
γi,j 0.0000 γi,j 0.0000 γi,j 0.0000
 0.0748  0.0717  0.1048
Methyl phenyl carbinol
Т = 320 К Т = 325 K Т = 330 К
σi,j 0.4126 σi,j 1.0386 σi,j 1.3622
βi,j 0.6670 βi,j 0.8831 βi,j 0.8675
γi,j 0.0000 γi,j 0.0027 γi,j 0.0039
 0.0073  0.1091  0.0428
Acetophenone
Т = 320 К Т = 325 K Т = 330 К
σi,j 1.6679 σi,j 1.7499 σi,j 1.4999
βi,j 1.1979 βi,j 1.2512 βi,j 1.2547
γi,j 1.4335 γi,j 1.6542 γi,j 1.7030
 0.0058  0.0062  0.0123
Table 6 and Figures 17 to 19 show the dependence of the solubility of styrene, methyl
phenyl carbinol and acetophenone, as well as the description according to the Peng-Robinson
equation of state with three adjustable parameters [21, 22]. From Figures 17 to 19, it is clear
that pollutants of the catalyst surface dissolved in supercritical carbon dioxide, therefore, it is
advisable to regenerate the catalyst alumina active by the presented method.
5. REGENERATION OF ACTIVE ALUMINA CATALYST USED

IN THE METHYL PHENYL CARBINOL DEHYDRATION PROCESS
BY SUPERCRITICAL CO2 EXTRACTION
The regeneration of the active alumina catalyst was carried out at 423.15 K, in the
pressure range from 10 to 30 MPa. The relative error of measurements does not exceed 12%.
The results of the investigation are shown in Figure 23.
Figure 23, shows that there is a reduction of the initial catalyst mass, suggesting a
possibility of regeneration of the catalyst by the method under consideration. A greater effect
can be obtained by modifying the operating parameters, and also the physical and chemical
nature of the extractant, in particular by changing with another polar additive. In addition, the
method of supercritical fluid extraction, in the regeneration process, will not cause the
destruction of the catalyst structure, which occurs in the case of the conventional catalyst
regeneration method [23].
The IR spectra of the samples of the regenerated catalyst (see Figure 24) confirm the
presence of changes, mainly the reduction of the number of deactivating compounds. For a
given catalyst, the most important area in the IR spectrum is the region between 1200 cm-1
and 800 cm-1, wherein the absorption bands of the compounds which reduce the catalytic
activity decrease more strongly. As indicated above, these are reaction products. Figure 24,
shows that the deactivated compounds, with absorption band in the region of 1400 cm-1, are
completely removed.
The absorption bands of 1260 cm–1 and 1210 cm–1 correspond to polar compounds such
as polymethyl siloxane and MPC esters, which due to the low dissolving capacity of pure SC-
CO2, cannot be completely eliminated.
Figure 20. Variation of the three binary interaction parameters  of styrene, in supercritical CO2,
in terms of temperature.
Figure 21. Variation of the three binary interaction parameters  of methyl phenyl carbinol, in
supercritical CO2, in terms of temperature.
However, the carbon dioxide dissolving capacity can be significantly increased by the
addition of polar co-solvents. The addition of a co-solvent also increases the yield of the
extract and form milder conditions of the extraction process [24]. The work in Reference [25]
has shown that polar compounds are poorly soluble in pure SC-CO2, while its dissolving
capacity increases considerably, by adding a polar modifier.
Figure 22. Variation of the three binary interaction parameters  of acetophenone, in supercritical
CO2, in terms of temperature.
Figure 23. Variation of the mass of catalyst in the regeneration method thereof as a function of the mass
of pure CO2, at T = 423.15 K, where P = 10 MPa, P = 20 MPa and P = 30 MPa.
The addition of 0.1 to 20 wt. % of modifiers such as methanol, ethanol and others, may
be performed before feeding the extractant into the extractor, or directly in the extractor. The
effect of co-solvents of a different nature on the change in mass of the catalyst, in the
regeneration process, has been studied on the above basis. Chloroform, methanol, acetone and
dimethyl sulfoxide (DMSO) were selected as co-solvents.
Figure 24. The IR spectra of chloroform extract of deactivated compounds for various catalyst samples
under study: (1) - fresh catalyst, (2) - deactivated catalyst, (3) - catalyst regenerated with pure SC-CO2,
(4) - catalyst regenerated with SC-CO2 + 2% DMSO.
Figure 25. Effect of different concentrations of co-solvent on the variation of the mass of catalyst in the
regeneration process at T = 343 K and P = 20 MPa: (1) - chloroform, (2) - ethanol, (3) – DMSO.
The concentration of co-solvents varied in the range of 1 to 9 wt. %. The results of

studies of the effect of different types of co-solvents, on the variation of the mass of catalyst,
in the regeneration process, performed at T = 343 K and P = 20 MPa are shown in Figure 25.
The catalyst mass change increases with increasing the concentration of co-solvent to the
first, reaches a maximum and then decreases. The value of the co-solvent concentration is
optimal in the range of 1.5 to 2.5 wt. %.
Figure 26. The mass change of the catalyst in the regeneration process thereof as a function of the mass
of the extractant: (1) - pure supercritical CO2;. (2) - supercritical CO2 + 2 wt. % DMSO.
Studies of variation of the mass of catalyst in the regeneration process, using supercritical
carbon dioxide modified with an optimal concentration of co-solvent was carried out at a
temperature T = 423 K and a pressure P = 20 MPa (Figure 26). The diagrams show that the
efficiency of regeneration was increased by 120%, by the addition of DMSO, due to the
removal of polar compounds.
This result was confirmed by the IR spectra of the chloroform extract of deactivation of
the catalyst composite samples, regenerated with pure and modified SC-CO2 (Figure 24).
6. COMPARISON OF THE CHARACTERISTICS OF THE SAMPLES

OF ACTIVE ALUMINA CATALYST REGENERATED BY THE
CONVENTIONAL APPROACH AND SC-CO2 EXTRACTION
The knowledge of the performance of active alumina catalyst is required to assess the
successful implementation of the supercritical fluid regeneration process.
As is known, the catalyst activity characterizes the change in reaction rate, with the
introduction of the catalyst into the reaction system. Sometimes, the activation energy, the
degree of reactant conversion, the reaction yield, the reaction time or the temperature at which
a certain degree of conversion is obtained are used as a measure of the activity of catalyst.
In this case, the conversion rate of methyl phenyl carbinol (MPC conversion) and
selectivity to styrene are used as criteria to measure the activity of the active alumina catalyst.
The main components of the MPC fraction are essentially methyl phenyl carbinol 80 to
82 wt. % and acetophenone 15 to 18 wt. %. In addition, the MPC fraction contains products
with higher boiling point, the total amount of which is defined as “heavy residue,” and the
total concentration thereof, in the initial mixture is 2.5 to 5 wt. %. The composition of heavy
residue includes compounds such as MPC ester or phenyl ethanol, which may react during the
reaction to form both styrene and MPC, a precursor to styrene, as well as to form higher
molecular oxygen condensed compounds or polystyrene. In this regard, the heavy residue
conversion was also evaluated at the same time, as the conversion of MPC, during the catalyst
test experiments.
The values of the conversion of MPC, the conversion of heavy residues and the values of
catalysts electivity of active alumina, calculated for the desired product, based on the
experimental data are presented in Table 7.
It is noted that the MPC conversion, for the fresh catalyst and the catalyst regenerated in
different ways are on the same level, but the regenerated catalysts are somewhat inferior to
the fresh catalyst for the conversion of heavy residues. Nevertheless, the regenerated catalyst
with pure supercritical CO2 shows a little more conversion than the catalyst regenerated with
the steam-air mixture.
After regeneration, the catalysts do not reach the fresh catalyst indicators by the
selectivity of the formation of styrene.
Nevertheless, the experimental data clearly show the advantage of the regeneration using
supercritical CO2. The selectivity of styrene formation, both, without considering or taking
into account the heavy residue is 6 to 7% higher, on the regenerated catalyst with pure
supercritical CO2, as compared with the catalyst regenerated with steam-air mixture.
The results of studies of the regeneration process of the active alumina catalyst, in
supercritical carbon dioxide media, suggest the possibility of a successful regeneration by this
method.
The regenerated catalyst with pure supercritical CO2 achieves MPC conversion and
reaches the value of the selectivity for styrene, and therefore, it restored the activity to higher
values than those of the steam-air regeneration; that indicates the effectiveness of the SCFE
process to extract deactivating substances from the surface of active alumina catalyst.
The dissolving capacity of pure carbon dioxide can be increased significantly by adding
polar co-solvent.
Thus, modification of SC-CO2 with DMSO polar co-solvent, allowed the elimination of
polar compounds, thereby reducing the amount of coke deposits.
Table 7. Values of conversion of MPC and heavy residue as well as

the selectivity of styrene formation
Catalyst regenerated
Fresh Catalyst regenerated
Structure with pure
catalyst with steam-air mixture
supercritical СО2
MPC conversion 99.80% 99.69% 99.77%
Heavy residue conversion, 75.01% 69.85% 70.44%
Selectivity of styrene
formation 100 mol.% 86.99 mol.% 93.97 mol.%
(on decomposed MPC)
Selectivity of styrene
103.9
formation (on decomposed 90.70 mol.% 97.69 mol.%
mol.%
MPC and heavy residue)
Thus, the supercritical fluid extraction process is a promising catalyst regeneration

method. Its application thereof, solves the problems of conventional high temperature
regeneration methods.
REFERENCES
[1] Kirpichnikov, P. A., Averko-Antonovich, L. A., Averko-Antonovich, Y. O. Chemistry,
Technology of Synthetic Rubber. Leningrad Chemistry, 1975: p. 480.
[2] Alumina Active State Standard # 8136-85, Standards Publisher, Moscow, 1985: p. 10.
[3] Satterfield, C. Practical Course in Heterogeneous Catalysis. Chemistry Publisher,
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[4] Masagutov, R. M., Morozov, B. F., Kutepov, B. I. Regeneration of Catalysts in Oil
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[5] Vasiliev, V. P. Analytical chemistry. Part 2: Physical and Chemical Methods of
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[6] Galimova, A. T., Sagdeev, A. A., Gumerov, F. M. Study of Solutes Deactivating Active
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68.
[7] Boyko, E. A. Complex Thermal Analysis of Solid Organic Fuels Monograph (2nd ed.),
Krasnoyarsk. 2006: p. 407.
[8] Galimova, A. T., Sagdeev, A. A., Kuzmin, V. Z., Gumerov, F. M. Investigation of the
process of regeneration of the catalyst active aluminum oxide in supercritical carbon
dioxide. Bulletin of Kazan. Technological University. 2013, 16, 1: 44-47.
[9] Smith, A. Applied IR Spectroscopy. Mir Publisher, Moscow, 1982: p. 328.
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Applications. CRC Press Publisher, Boca Raton, FL, 1991: p. 593.
[11] Tukhvatova, A. T., Kayumov, R. A., Khairutdinov, V. F., Sagdeev, A. A., Sarimov, N.
N., Gumerov, F. M., Gabitov, F. R., Volfson, S. I. The Solubility of Styrene in
Supercritical Carbone Dioxide. Russian Journal of Physical Chemistry B, 2010, 4, 8:
1252-1264.
[12] A Utility Model Patent of the Russian Federation n° 99340 “Unit for the Research of
Solubility of Substances with the Use of Supercritical Fluids,” publ. 20/11/2010.
[13] Galimova-Tuhvatova, A. T., Sagdeev, A. A., Gumerov, F. M. The Behavior of the
Solubility of Styrene in Supercritical CO2. Bulletin of Kazan Technological University.
2010, 8: 51-54.
[14] Galimova, A. T., Sagdeev, A. A., Gumerov, F. M. Solubility of Methyl Phenyl Carbinol
Acetophenone in Supercritical Carbon Dioxide. Bulletin of Kazan Technological
University. 2013, 16, 5: 296-298.
[15] Van Ness, H. C., Abbott, M. M. Vapor-Liquid Equilibrium. Part VI. Standard State
Fugacity for Supercritical Components. AIChE J., 1979, 25, 4: 645-653.
[16] Sato, Y., Tkikawa, T., Takishima, S., Masuoka, H. Solubilities and Diffusion
Coefficients of Carbon Dioxide in Polyvinyl Acetate and Polystyrene. J. of
Supercritical Fluids. 2001, 19: 187-198.
[17] Galimova-Tukhvatova, A. T., Sagdeev, A. A., Sarimov, N. N., Gumerov, F. M.
Description of the Styrene Solubility with SC-CO2 Using Peng - Robinson's Equation.
XVII International Conference on Chemical Thermodynamics in Russia. Kazan. 2009:
462.
[18] Galimova-Tuhvatova, A. T., Sarimov, N. N., Sagdeev, A. A., Gumerov, F. M.
Solubility of Styrene in Supercritical Carbon Dioxide. Bulletin of Kazan Technological
University. 2009, Part I, 3: 30-38.
[19] Ashour, I., Almehaideb, R., Fateen, S. E., Aly, G. Representation of Solid-Supercritical
Phase Equilibria Using Cubic Equation of State. Fluid Phase Equil. 2000, 167: 41.
[20] Galimova-Tuhvatova, A. T., Sarimov, N. N, Sagdeev, A. A., Gumerov, F. M. Solubility
of Styrene in Supercritical Carbon Dioxide. V International Scientific and Practical
Conference “Supercritical Fluids: Fundamentals, Technology and Innovation.” Suzdal.
2009: 205.
[21] Galimova-Tuhvatova, A. T., Sagdeev, A. A., Gumerov, F. M. Solubility of
Acetophenone and Methyl Phenyl Carbinol in Supercritical CO2. VI All-Russian
Scientific Student Conference “Intensification of Heat and Mass Transfer Processes in
Chemical Engineering.” Kazan. 2010: 121-123.
[22] Galimova, A. T., Kayumov, R. A., Sagdeev, A. A., Gumerov, F. M. Solubility in
Supercritical CO2 Process Waste Component and Styrene Co-production of Propylene
Oxide. Proceedings of the VI Scientific and Practical Conference “Supercritical fluids

(SCF): Fundamental Base, Technology and Innovation.” Listvyanka village, 2011:
237-238.
[23] Tyapkin, E. V., Sharafutdinov, I. R., Gumerov, F. M. Regeneration of PU Brand
Palladium Catalyst with the Use of Supercritical Extraction Process. III International
Scientific and Practical Conference “Supercritical Fluid Technologies: the Innovative
Potential of Russia”: Abstracts, Rostov, 2006: 67-69.
[24] Gumerov, F. M., Sabirzyanov, A. N., Gumerova, G. I. Sub- and Supercritical Fluids in
Polymer Processing. Fen Publisher, Kazan, 2007: p. 336.
[25] Gumerov, F. M., Sabirzyanov, A. N., Gumerova, G. I. et al. Prospects of Sub- and
Supercritical Extragents Usage in Metal Recovery from Bitumen and Highly Viscous
Oils. Chemistry and Computational Simulation. Butlerov Messages 2004, 5, 1: 9-15.
Chapter 4
REGENERATION OF LD-265 PALLADIUM CATALYST

USED IN THE HYDROGENATION OF DIENE
HYDROCARBONS BY SUPERCRITICAL
CO2 EXTRACTION
K. A. Sagdeev1, A. A. Sagdeev1, F. M. Gumerov2,*,

Z. I. Zaripov2 and B. Le Neindre3
1
FederalState Educational Institution of Higher Professional Education Nizhnekamsk
Chemical Technology Institute, Nizhnekamsk, Russia
2
Federal State Educational Institution of Higher Professional Education,
3
Sorbonne Paris Cité, Laboratoire des Sciences des Procédés et des Matériaux,
Villetaneuse, France
ABSTRACT
The nature of deactivating deposits formed on the LD-265 palladium catalyst used in
the hydrogenation of diene hydrocarbons is analyzed. Solubility of one of them:
polyisoprene, was measured in supercritical carbon dioxide in the temperature range from
343 to 393 K and pressures from 20 to 34 MPa. Heat capacity and enthalpy of mixing of
polyisoprene in supercritical carbon dioxide was also measured. The possibility of
regeneration of the catalyst using pure supercritical carbon dioxide and supercritical
carbon dioxide modified by polar additive is investigated at 343 and 423 K, in the
pressure range 10-30 MPa. The kinetic of the catalyst regeneration with SC-CO2 was
studied. A comparison of the activities of traditionally regenerated and regenerated with
SC-CO2 catalyst samples showed that the method suggested is very competitive
compared to traditional regeneration techniques.
Keywords: catalyst regeneration, catalyst activity, palladium catalyst, supercritical carbon

dioxide, heat capacity, enthalpy of mixing
*
Email: gum@kstu.ru.
78 K. A. Sagdeev, A. A. Sagdeev, F. M. Gumerov et al.
1. INTRODUCTION
A diene is a hydrocarbon chain having two double bonds which may or may not be
adjacent to each other. The arrangements of these double bonds can have variable effects on
the reactivity and stability of the compounds. Hydrogenation is the reaction of hydrogen with
a carbon-carbon multiple bond to saturate the compound. This reaction has long been known
and is usually carried out at high pressures and moderate temperatures using a large excess of
hydrogen over a metal catalyst.
In petroleum processing, by fluid catalytic cracking of petroleum fractions, oil refineries
contain a wide range of olefins and aromatic compounds. The main type of alkene made, and
the nature and concentrations of the polyunsaturated, depends on the severity of the steam -
cracking. In general, under moderate conditions of temperature (below about 810 K), time
and pressure, mono-olefins are formed in larger amounts. These unsaturated compounds
comprise ethylene, acetylene, propylene, propadiene, methyl acetylene, butene, butadiene,
amylene, hexene etc. Many of these compounds are valuable, especially as feedstocks for
chemical products.
Olefins are the basis for polymers and oligomers used in plastics, resins, fibers,
elastomers, lubricants, and gels. 1,3-butadiene is a precursor to rubber used in tires and
isoprene also known as 2-methyl-1,3-butadiene is used as a monomer to produce
polyisoprene for car tires, footwear, mechanical products, sealing and caulking compounds.
Aromatic fractions (BTX) are produced by processes such as naphtha reforming and
thermal cracking (pyrolysis). The mechanism generally considered for the hydrogenation of
aromatic compounds is an ingenious step reaction between the adsorbed aromatics (BTX) and
the desorbed hydrogen gas. The aromatic fractions are used as feedstocks in various
petrochemical processes.
However, the olefins having more than one double bond and the acetylenic compounds
(having a triple bond) have less uses and are detrimental to many of the chemical process
wherein the single double bond compounds are used, for example polymerization.
Among the metals known to catalyze the hydrogenation reaction of unsaturated
hydrocarbons are platinum, rhenium, cobalt, molybdenum, nickel, tungsten and palladium.
Nickel and palladium metals have good activity, selectivity and a high potential for migration
of the double bonds. Generally, commercial forms of catalyst supports are oxides. The oxide
is reduced to the active form either prior to use with a reducing agent or during operation by
the hydrogen in the feed. Alumina is very stable, has a reasonable surface area and is
relatively inexpensive, so is typically used for this process.
In this study, the exhaustive process of hydrogenation of diene hydrocarbons, in BTX
fraction, was performed using LD-265 alumina support palladium catalyst from Axens.
Industrially, catalytic performance of supported palladium catalysts strongly depends on the
morphology and dispersion of Pd particles. Pd active-sites isolation is the principal objective
to use porous oxide supports. Although porous oxide supports can provide a large surface
area to form small Pd particles, however, narrow and long pores in porous oxide supports
might hinder the transport of reactants and products. Therefore, in the tail-end hydrogenation
process, supported palladium catalysts have low stability due to the formation of green oil by
oligomerization of alkenes, polyenes, and/or alkynes on the solid catalyst surfaces. Green oil,
as used herein, refers to molecules having six or more carbon atoms per molecule and is
Regeneration of LD-265 Palladium Catalyst … 79
undesirable in the production of an alkene, as it fouls the hydrogenation catalyst which in turn
deactivates the catalyst. The deactivation process can reduce the activity and selectivity of the
catalyst.
The presence of the polyunsaturated compounds is highly undesirable, as they interfere
with further processing of the alkenes, because of their ready oxidation or oligomerisation (in
the case of dienes) or their toxicity to catalyst (in the case of alkynes).
The most common way of estimating the parameters of the porous system of the
catalysts, the values of specific surface area, the total pore volume, the shape of the pores, the
average pore size and distribution of pore sizes is a method of nitrogen adsorption at low-
temperature.
There are a large number of reactive species in the feedstock, which can easily contain
150 to 200 components and thus identification and separation of the components is difficult;
some of them can be polymerized to form coke during the reaction. The coke deposits on the
catalyst, block the active sites and reduce the accessibility of reactant to these sites. The
accumulation of coke in pores may also fracture the support, which must be inert to the
polymerization reactions. In addition to the hydrogenation reactions of diene and alkenyl
aromatic hydrocarbons, a second-order catalytic reaction took place on the catalyst surface:
oligomerization of unsaturated compounds on acid-base centers of aluminum oxide. The
resulting oligomers deactivate the catalyst, reducing its hydrogenation activity and the
duration of the inter-regeneration period.
Deactivation by carbonization of the surface cannot be completely avoided, as it is
conditioned by the occurrence of hydrogenation reactions of unsaturated hydrocarbons in
oligomerization processes. High operating temperature of the catalyst leads to a decrease of
the specific surface area and porosity. In some cases, not only the support but also the metal is
subjected to sintering.
Spent catalysts can be regenerated or reactivated by different physical, chemical and
thermal methods. The conventional methods of regeneration using a gas containing oxygen or
by thermal treatment with live steam represent several steps, time and energy consuming, in
the processes. In addition, the application of a high temperature may cause sintering of the
support; partial removal of compaction products from the surface of the catalyst, but does not
yield the catalyst with an activity close to initial.
The aim of the present study was to evaluate the possibility of regenerating a spent
alumina support palladium catalyst using supercritical carbon dioxide extraction, either pure
or with co-solvents. Samples of discarded alumina support palladium catalysts pretreated with
a steam-air mixture are obtained from hydrogenation reactors of Nizhnekamskneftekhim JSC,
when they were replaced at the end of the operating cycle.
The catalyst samples were extracted with pure supercritical carbon dioxide, and the
regeneration was also performed with supercritical CO2 modified by 6 wt. % of ethanol and
with supercritical CO2 modified by 6 wt. % of DMSO. It was expected that increasing the
polarity of the extraction solvent with supercritical CO2 modified with polar co-solvents,
would favor the removal of polar compounds. The regeneration by supercritical CO2,
modified with 6 wt. % of DMSO, gives the best results and leads to a significant reduction of
the content of compaction products on the catalyst surface.
The results of our investigations indicate that regeneration of a spent Pd/Al2O3 catalyst
have produced an almost complete removal of by-products, the purification of the catalyst
surface, and the restoration of the original form of the palladium; thus, it was possible to
recover a catalytic activity nearly comparable with that of the fresh catalyst. The
implementation of this technique seems to be relatively straightforward and also relatively
inexpensive.
2. HYDROGENATION OF DIENE HYDROCARBONS, CHARACTERISTICS

OF SPENT CATALYST AND DESCRIPTION OF ITS CONVENTIONAL
REGENERATION PROCESS
In petroleum processing, aromatic fractions are derived from processes such as naphtha
reforming and thermal cracking (pyrolysis). In this process a naphtha rich in C5 to C9 alkanes
is reacted at about 723 K and 2 to 3 MPa, over a Pt/SiO2 catalyst, to give reaction products
that are about 60% aromatic hydrocarbons. Typically, the products might contain 3%
benzene, 12% toluene, 18% xylenes, and 27% of C9 alkylbenzenes (which have high octane
numbers and are mixed into gasoline). The aromatic streams are used as feedstocks in various
petrochemical processes.
The importance of aromatic streams for the petrochemical industries is related to their
activities as chemical compounds, which can be alkylated, oxidized or hydrogenated to give a
great number of useful chemical and intermediates. Benzene, toluene and xylene (BTX) are
used for the production of polymers, other chemicals, and many consumer products (solvents,
paints, varnishes, pharmaceuticals). Benzene, for instance, is a component of gasoline fuel but
it is also a starting material for production of ethylbenzene, cumene, cyclohexane, aniline and
chlorobenzene.
The aromatic compounds are responsible for the high octane rating of reformed gasoline.
However, in recent years, increased fuel regulations have reduced the maximum content of
aromatic compounds allowed in gasoline to less than 35%, according to the gasoline
specification of the European Union. The BTX compounds are hydrogenated, either to reduce
their content in the gasoline fraction, or to make saturated compounds (cycloalkane). The
rates of hydrogenation of aromatics generally decrease with alkyl-substitutions, and follow
the order: benzene ≥ toluene > o-xylene.
The group VIII metals catalysts (Ni, Pd and Pt) are generally used as active agents for
hydrogenation of unsaturated hydrocarbons. The classification of metals according to their
hydrogenation activity and selectivity is complex, since they depend on various factors such
as catalyst and reaction parameters. Nickel and palladium metals have good activity,
selectivity and a high potential for migration of the double bonds.
The mechanism generally considered for the hydrogenation of aromatics is a judicious
step reaction between adsorbed aromatics (benzene, toluene) and the desorbed hydrogen gas.
A complete hydrogenation is not always desired and selective hydrogenation can be achieved
by using an appropriate catalyst and control of the reaction parameters.
Due to the large amount of reactive species in the feedstock, some of them can be
polymerized to form coke during the reaction. The deposition of coke on catalyst, block the
active sites and reduce the accessibility of reactant to these sites. The accumulation of coke in
pores may also fracture the support, which must be inert to polymerization reactions. Then,
the regeneration of catalyst and the combustion of carbonaceous material deposited on the
surface of catalyst should be performed periodically.
Table 1. Physical and chemical characteristics of the catalyst
Characteristics LD-265
Appearance Light-brown beads
Bead diameter 2-4 mm
Palladium content 0.3 wt. %
Bulk density 660 kg/m3
Crushing strength, not less than 1.55 MPa
Specific surface area 70 m2/g
Therefore the catalyst should be mechanically and thermally stable in order to undergo
several regenerations at high temperature. Alumina is very stable, has a reasonable surface
area and is relatively inexpensive, so is generally used for this process.
The process of exhaustive hydrogenation of diene hydrocarbons, in benzene-toluene-
xylene fraction, was carried out using LD-265 alumina support palladium catalyst from
Axens.
The physical and chemical characteristics of the catalyst are reported in Table 1 [1]. The
process is carried out in liquid phase, at a pressure from 4.6 to 4.7 MPa, with a reactor inlet
temperature of 323 - 413 K. The volumetric feed rate was m3/h, the hydrogen flow rate 100
m3 per m3 of raw material, and the ratio of raw materials to the recycle one varies from 0.25
to 0.17 [2-3].
The ratio of consumption of raw material and recycling in the reactor was chosen so as to
reduce harmful effects of oligomerization of unsaturated hydrocarbons. The main
hydrogenation reactions can be represented by the following schemes [4]:
The hydrogenation of unsaturated hydrocarbons is based on the difference in reactivity of

the unsaturated bonds. These hydrocarbons are classified according to their activity, as a
function of the addition of hydrogen, under pressure in the presence of the catalysts:
acetylene > diene > vinylarene > olefin > naphthalene > benzene.
The hydrogenation process of unsaturated compounds in the BTX fraction is
accompanied by the release of thermal energy and the decrease in volume due to hydrogen
absorption. From a thermodynamic point of view, to increase the degree of conversion at
equilibrium, it is desirable to carry out these reactions at high pressure and relatively low
temperature.
Consider the feedback mechanism of hydrogenation of diene hydrocarbons, on the
surface of metallic palladium, taking as an example: cyclopentadiene and styrene.
+Н2
Pd (Н) Pd (Н)
+Н2
Pd (Н) Pd (Н)
Figure 1. Chain reactions during hydrogenation of cyclopentadiene.
Cyclopentadiene (CPD) is a representative of cyclodiolefins. Cyclopentadiene monomer

may be produced in substantial quantities from dicyclopentadiene recover from by-product of
naphta steam-cracking. The conjugated double bonds system of CPD is responsible for its
high reactivity. Monomeric cyclopentadiene is unstable, and then extreme care must be taken
in the treatment of monomer cyclopentadiene. It is well known that the monomer quickly
returns to its dimer state. At 310 K, for example, 12 percent of a given amount of monomer
dimerize in less than 20 minutes. As expected, the polymerization is much faster at higher
temperatures. It is therefore necessary to selectively hydrogenate diolen under conditions that
minimize both the formation of any substantial amount of saturated cyclic product and
dimerization of diene.
CPD is hydrogenated in cyclopentene and further cyclopentane following the reaction
shown in Figure 1. Cyclopentene is a basic product for the preparation of cyclic aldehydes,
alcohols, chloro-compounds, and fuels.
Hydrogenation of CPD in cyclopentene, in the same manner that the hydrogenization of
cyclopentene to cyclopentane, is the first order reaction. At temperatures below 600 K, the
equilibrium of the consecutive reaction of CPD hydrogenation to cyclopentane is almost
completely shifted towards the formation of cyclopentane. It is known that in the case of CPD
hydrogenation at lower temperatures, the yield of cyclopentene is 100% [5].
Since cyclopentene is easily hydrogenated to cyclopentane, the average conversion of
olefins to paraffins is in the range of 10 to 20%. Hydrogenation reaction takes place in these
cases, far from thermodynamic equilibrium, and the product yield is determined by the
kinetics of the reaction.
The hydrogenation of styrene containing unsaturated (vinyl) side chain, and phenyl
radical has been chosen for its practical interest but also for theoretical interest due to its two
unsaturated systems energetically non-equivalent. The styrene hydrogenation can occur
selectively to ethylbenzene or unselectively to ethylbenzene and ethylcyclohexane.
Styrene can be hydrogenated selectively to ethylbenzene according to the following
scheme (Figure 2) [6].
In addition to the hydrogenation reactions of diene and alkenyl aromatic hydrocarbons, a
second-order catalytic reactions took place on the catalyst surface: oligomerization of
unsaturated compounds on acid-base centers of aluminum oxide. The resulting oligomers
deactivate the catalyst, reducing its hydrogenation activity and the duration of the
inter-regeneration period.
Figure 2. Mechanism of hydrogenation reaction of styrene to ethylbenzene.
The possible mechanisms of deactivation of these kinds of hydrogenation catalysts are

many. However, they are essentially of three types: chemical, mechanical and thermal [7].
1) Chemical nature:
- Poisoning due to the strong chemisorption of species coming from the feed
stream, on catalytic sites, which block sites for catalytic reaction.
- Chemical reaction of gas with catalyst phase to produce volatile compound.
- Chemical reaction of fluid or support with catalytic phase to produce inactive
phase.
2) Mechanical nature
- Physical deposition of species from fluid phase onto the catalytic surface and in
catalyst pores (fouling).
- Mechanical loss of catalytic material due to abrasion
3) Thermal nature
- The loss of the catalytic surface area, support area, and the active phase support
reactions induced by heat.
A major cause for the decrease of activity of the palladium catalyst is morphological
changes of palladium entities due to the growth of particles, the deposition of coke and coke
transformation, the influence of the support material on long-term stability, the modification
of the surface of the palladium, including the valence changes or the formation of stable
organometallic species on the surface, and the change in physical properties as well as
chemical poisoning, corrosion or leaching [8].
In industrial operations, the poisoning of the catalyst is prevented by the use of special
techniques: cleaning of the feed streams from catalytic poisons, using preliminary catalytic
purifiers. Deactivation by carbonization of the surface cannot be completely avoided, as it is
conditioned by the occurrence of hydrogenation reactions of unsaturated hydrocarbons in
oligomerization processes. Growth of oligomers occurs both on the surface of the palladium
particle and the oxide support, and the number of oligomers formed on metal particle is
several orders smaller than the content of condensates on the surface of the support. During
operation, the degree of unsaturation of condensed structures increases with decreasing H/C
ratio, which are not hydrogenated under mild reaction conditions, and not desorbed from the
surface of the active component. The reduction in the catalyst activity depends largely on the
rate of formation of resin-like structures [9]. High operating temperature of the catalyst leads
to a decrease of the specific surface area and porosity. In some cases, not only the support but
also the metal is subjected to sintering [10]. Under industrial conditions, the conventional
catalyst regeneration includes the following steps [11]:
- Purging with cold methane or nitrogen, to free catalyst pores from raw materials and
hydrogen;
- Heating up to 473 K of all the catalyst layers, with methane or hot nitrogen to
prevent condensation of steam;
- Streaming of the catalyst with steam at 523 K for 10 to 15 hours, to remove the
greatest amount of resins and polymers from the surface of the catalyst beads;
- Pre-oxidation (combustion) of polymers by the mixture of steam and air; the amount
of oxygen in air is adjusted to 0.5 vol. %, in the mixture of the flow of regeneration,
to the inlet of the reactor at a temperature of 523 K for 2 hours;
- Increasing the temperature with steam, to intensify the combustion of polymer and
resin residues in the pores of the catalyst beads:
a) At the reactor inlet temperature of 673 K, air flow rate to the steam regeneration
increases from 0.1 to 3 vol. %, of oxygen, in steps of 0.2 to 0.3 vol. %. Air flow
rate to steam regeneration is increased moderately, so that the temperature
flashes in the catalyst layers (ΔT), due to the combustion of polymer and resin
residues, does not exceed 323 to 333 K;
b) At the reactor inlet temperature of 733 K (maximum 753 K), air flow rate to the
steam regeneration is maintained to 3 vol. % of oxygen. The combustion is
completed in the absence of change in the temperature of the catalyst layers,
when flashes of ignition of resins and polymers stop, and CO2 content in the
outlet flow of regeneration gas drops to zero.
- Cooling of reactor to 623 K (and not below) by steam, in order to prevent
condensation on the surface of the catalyst;
- Hot methane (nitrogen) drying at a dew point, in the outlet of purge gas from the
reactor, does not exceed 343 K;
- Cooling with methane (nitrogen) to 338 K. The purge with nitrogen to oxygen
content in the purge gas outlet does not exceed 0.5 vol. %.
As is evident from the foregoing, the conventional methods using a regeneration gas
containing oxygen or by a thermal treatment with live steam, represent several steps, time and
energy consuming, in the processes. In addition, the application of a high temperature may
cause sintering of the support; partial removal of compaction products from the surface of the
catalyst, but does not yield the catalyst with an activity close to initial.
Therefore, the possibility of catalyst regeneration using the process of supercritical fluid
extraction (SCFE), for example using supercritical carbon dioxide either pure or with co-
solvents, is currently of great interest to researchers. This research applied to the selective
hydrogenation of catalysts has been conducted by the authors of several studies [12-14].

Samples of discarded alumina support palladium catalysts pretreated with a steam-air
mixture are obtained from hydrogenation reactors of Nizhnekamsk neftekhim JSC, when they
were replaced at the end of the operating cycle.
To implement the study of supercritical fluid extraction process, using pure and modified
extraction agent, an experimental setup (Figure 3) was developed and built, it is protected by
a patent of the Russian Federation [15].
The installation comprises a high pressure plunger pump (Waters P50A), which provides
a fixed flow rate of solvent in the range of 1 to 50 g/min, at a pressure up to 60 MPa. For
normal operation of the pump, liquid carbon dioxide is supplied to the suction circuit. Gas
liquefaction occurs in the refrigerator and directly in the pump by a coolant circulation in the
cooling jacket of the pump and annular space in the refrigerator. The temperature, at which
the cooling unit cools the coolant (258 K), is controlled by a chromel-copel thermocouple
mounted in the refrigerator.
13 8 9 7 3 2 4 1
ТЕ
ТЕ
12 11b 11a 10 6 5
Figure 3. Diagram of the experimental setup: (1) - carbon dioxide cylinder; (2) - refrigerator; (3) - high-
pressure pump (Waters P50A); (4) - refrigeration unit; (5) - container for co-solvent; (6) - high-pressure
pump (LIQUPUMP 312/1); (7) - three-way valve; (8) - extraction cell; (9) - heat exchanger; (10) -
electronic measuring and controlling device (2ТRM1); (11a), (11b) - collectors of extracts; (12) -
thermostatic bath; (13) - throttle valves.
Co-solvent is supplied from the container by a high-pressure plunger pump (LIQUPUMP

312/1), providing a fixed flow rate of co-solvent in the range of 0.01 to 9.99 сm3/min, to give
the required concentration of 2 to 10%, of modifier in supercritical CO2. A design feature of
the pumps remains two pump heads, with pistons constantly working, smoothing solvent and
co-solvent flow pulsating, and thereby achieving a high degree of uniformity of their feeding.
To prevent the return of CO2 and co-solvent back to the pumps, check valves are used.
The extraction cell is a high pressure vessel divided into two parts. In one part the solids
are extracted, in the other part the liquids are extracted. The cell is mounted into the heat
exchanger, which is a thick-walled copper tube, on which a heating coils and a pipeline is
laid. The solvent supplied for extraction is preheated. This design allows a maximum
reduction of temperature gradients within the cell, due to a uniform heating of the cell and the
preheating of the solvent supplied. Two temperature sensors are mounted in the cell, one of
which is located directly on the cell body and the other on the heat exchanger. The signals
from the sensors are transferred to an electronic measuring and controlling device (2TRM1),
which maintains the temperature with an accuracy of ± 0.25 K. The surface of the heat
exchanger is covered with thermal insulating sheets.
Extract collectors in the form of high pressure vessels with replaceable cartridges
containing the extract within, are placed in a thermostatic bath. Throttle valves which act as a
restrictor, allow the fractionation of the mixture by the pressure variations.
In order to determine the degree of extraction of compacting products, the dead catalyst is
weighed before and after the experiment.
To ensure a high degree of saturation of supercritical solvent in the investigated sample,
the optimum flow rate is adjusted on the basis of a preliminary study, of the effect of the mass
flow rate of supercritical CO2, on dead catalyst mass change (Figure 4).
As seen on the graph, the optimum flow rate of the supercritical solvent is in the range of
1 to 1.6 g/min.
In addition, within the scope of this study, to demonstrate the efficiency of SCFE, the
activity of regenerated catalysts was measured on the flow-circulation setup shown in
Figure 5.
The main element of the flow-circulation system is a flow reactor (1), with a fixed
catalyst bed. The reactor is configured in the form of a cylindrical metal tube of 500 mm in
height, with an internal diameter of 25 mm. Pipe material is high-alloy stainless steel.
To obtain a more uniform distribution of the feed over the entire length of the reactor, the
quartz layer is laid over and under the catalyst bed.
Heating of the reactor was carried out by heating elements wound spirally, such that the
average temperature of the reactor filled with catalyst, was uniform. The temperature in the
catalyst bed was monitored with Pt-100 platinum resistance thermometers. The accuracy of
temperature measurement was ± 0.5 K.
Before testing, each sample was first restored in a hydrogen atmosphere, at a rate of a
temperature increase of 50 K per hour, up to 433 K, and maintained at this temperature for 8
hours. Tests were carried out in a laboratory reactor, in the real medium of raw material of
BTX fraction, the hydrogenation in the liquid phase was performed under identical conditions
for all samples, under the following process conditions:
- Pressure: 4 MPa;
- Feed space velocity: 2.5 h-1;
- Hydrogen volumetric flow rate: 500 сm3/min;

- Inlet temperature of the process: 313 K;
- Catalyst volume: 50 сm3.
Figure 4. Variation of the mass of alumina-palladium catalyst as a function of the mass flow rate of
supercritical СО2 (T = 423 K and P = 20 MPa).
Feed N2
stock
20
25
12 5 19
H2
РI
26 30
13 14
РI 23
11 27
31 Water
28
РI 22
16 Water
21
29
2 РI 18
6
17
9 1
10
Gaseous product into
Fume extraction hood
4 3
15
7 8 24
N2 H2
32
Water Water
Liquid product
to collector
Figure 5. Schematic diagram of the flow-circulation system for the study of heterogeneous catalytic
processes: (1) - reactor, (2) - refrigerator, (3) - liquid separator, (4) - buffer tank, (5) - metering vessel,
(6) - metering pump, (7) - nitrogen cylinder, (8) - hydrogen balloon, (9) - nitrogen reducer, (10) -
hydrogen reducer, (11) - nitrogen drier, (12) - preliminary catalytic purifier, (13) - gas filter, (14) - gas
dehumidifier, (15) - gas meter, (16) - helical line in red copper, 17 - container for condensate, (18) -
thermostat, (19-29) - valves, (30-32) - fine adjustment valves.
The catalyst activity was monitored by diene and bromine numbers, characterizing the
content of diene, and unsaturated hydrocarbons, in the hydrogenated product.
The heat capacity of deactivating compounds was studied on the automated experimental
setup, made on the basis of scanning calorimeter (ITS-400) [16, 17].
The formula used for calculation is as follows:
m' '    0
CP ( P, T )  CP'' ( P, T ). . , (1)
m  ''   0
''
where CP ( P, T ) and CP ( P, T ) (in J/(kg.K) are the isobaric heat capacities of the test
sample and the reference sample, under the pressure P and the temperature T; m and m''
(in kg) are the masses of the sample and the reference substance; τ and τ' (in sec) are the delay
times of measuring thermocouples for the test and the reference samples respectively; τ0 (in
sec) is the time delay measured by the thermocouples in the empty cell.
The results of the measurements of the heat capacity of stearic acid (purity: 99.9%), at
atmospheric pressure, are shown in Figure 6.a. The variation of the heat capacity of n-butyl
alcohol (nD20 = 1.3995, ρ25 = 809.5 kg/m3), at pressures ranging up to 18.4 MPa as a function
of temperature and the comparison with literature data are presented in Figure 6.b. ( The
pressure of the system increases when the temperature increases). Cp deviations of stearic acid
from literature data [18] before the melting point (342.4 K), do not exceed 2.1%, and for n-
butyl alcohol, the deviations do not exceed 2 to 3% [19, 20]. The latent heat of the first order
liquid-crystal phase transition, calculated on the basis of the resulting values of stearic acid
heat capacity is 61.6 kJ/(mol·K), the deviations from the literature data [18] are only 0.7%.
Figure 6. a. Heat capacity of stearic acid, at atmospheric pressure as a function of temperature and
comparisons with literature data: ■ – author,  – [18].
Figure 6. b. Heat capacity of n-butyl alcohol, as a function of temperature and comparisons with
literature data: ■ – authors,  – [19, 20].
Figure 7. Diagram of the experimental heat-conducting calorimeter: (1) - gas cylinder; (2) - dryer; (3) -
thermo-compressor; (4) - dead weight pressure gauge; (5), (6) - amount of gas measuring system; (7) -
micro-calorimeter; (8) - temperature control system.
The uncertainty of measurement of the heat capacity does not exceed  2% to a level of
confidence of 95%.
Thermal effects related to the processing of materials by supercritical carbon dioxide are
studied on the experimental setup, implementing the method of heat-conducting calorimeter
[21] (Figure 7), with automatic data collection and processing [22]. The design of large units
of this configuration is described in detail in [22-25].
The purpose of the measurement method is to determine the value of the heat flow, which
arrives from the cell, and powers the thermoelectric battery in the micro-calorimetric
elements. This heat flow, which is produced in the cell, is due to the heat generated or
absorbed by the cell contents, during mixing or dissolution, and the heat of compression or
expansion.
Formula for calculating the occurring thermal mixing effect (dissolution) H mix is as
follows [26]:
Fmix  F f
H mix 
  , (2)
where Hmix is the heat of mixing (dissolution) (in J/mol); Ff and Fmix are (in (V·sec), the areas
of the thermograms of gas and gas mixture, (SCO2  cos ) ; η ( in mole) is the amount of
substance or gas;  (in μV/mW) is the sensitivity of the thermoelectric battery.
Figure 8. Results of the measurements of the enthalpy of dissolution of CO2-H2O binary mixture: P = 2
MPa (1) - [26], (2) - authors; P = 10.5 MPa, (3) - [23], (4) - authors; P = 20.8 MPa , (5) - [26], (6) -
authors.
To confirm the accuracy of these studies, the control measurements of the enthalpy, of
CO2-H2O binary mixture, were performed (Figure 8), supplies with reliable experimental data
[26]. The accuracy of the resulting thermal effects is confirmed by the control measurements
of the enthalpy of dissolution of CO2-H2O binary system. The deviation between the results
of our measurements and literature data is not more than 6.9%. The uncertainty of the
measurement of the heat of dissolution does not exceed  3%, at a 95% confidence level.
Methodology of the Experiments
The thermal effects of the dissolution of gas (fluid)-solid mixture were measured in the
cell described in [22, 24].
The measuring cell is carefully washed, weighed on an analytical balance (VLTE-150)
(accuracy class II), and the test substance is placed in it. The cell is weighed again, then
placed in the micro-calorimeter, and connected to the pressure generating system. Then the
operating pressure is set by the thermo-compressor.
The measurements are performed after reaching steady state conditions. Time to reach
steady state conditions depends on the temperature of the experiment, ranging from 2.5 to 6
hours.
The test parameters are set to the control program before the measurements. Before the
measurements, experimental zero is checked. If the zero drift does not exceed 10-20 mV for
40 minutes, the program starts. Then, the gas is introduced into the cell, with the test
substance through the high pressure valve, and the sample is saturated. Saturation process
occurs at a constant pressure and is accompanied by a change in temperature that is recorded
by the differential thermoelectric battery integrated in the measurement circuit.
The amplified signal of differential thermocouples received from the bridge circuit, by
fast cyclical scanning of ADC monitoring type, is converted and transmitted to the computer.
Each value is the average of 10 values, recorded at a given point in time. During the
experiment, the collection of experimental points is accumulated, and stored in the data file.
A method to equalize the temperature of the liquid in the cell is controlled by the
thermoelectric batteries.
After the measurements, the program proceeds to further processing. The program
provides for the calculation of the thermogram area, corresponding to the heat flux from the
cell. In the process of measurement and treatment, the information is displayed on the screen,
in a convenient form for the operator. At the end of the measurements, the pressure is released
and the thermal processes occurring are recorded, followed by calculation of these values.
4. SOLUBILITY OF CATALYST DEACTIVATION COMPOUNDS

IN SUPERCRITICAL CO2
To perform supercritical fluid extraction process, in order to regenerate LD-265

palladium catalyst, it is necessary to investigate the solubility of compounds of the
deactivation in supercritical carbon dioxide.
Infrared spectroscopic study of the spent catalyst sample was conducted to determine the
nature of deactivation compounds [1]. Compaction products adsorbed on the support are
styrene oligomers, dicyclopentadiene and condensed aromatic hydrocarbons. The greatest
contribution to the deposits is due to oligomerization products of styrene and
dicyclopentadiene.
As the least stable unsaturated hydrocarbons are hydrogenated on this catalyst, such as
isoprene, piperylene, cyclopentadiene, styrene, it is impossible to avoid their oligomerisation
and polymerisation on the surface of the catalyst. Therefore, the polyisoprene has been
chosen as a research topic. Solubility of styrene in supercritical carbon dioxide has been
studied previously in [27, 28].
Firstly, the effect of mass flow rate of supercritical CO2, on polyisoprene solubility, in a
solvent was examined (Figure 9). The optimum solvent flow rate was determined in the range
of 1 to 1.3 g/min, which corresponds to the equilibrium concentration.
The effect of pressure on the polyisoprene solubility in pure supercritical CO2 is shown in
Figure 10. With increasing pressure from 20 to 30 MPa, there is a significant increase in the
solubility. Further increase in pressure has no significant effect. Isotherm T = 393 K is clearly
above the rest, thanks to a better softening of polyisoprene and therefore, its greater solubility
in supercritical CO2.
The nature and concentration of the co-solvent in supercritical CO2 have an effect on the
solubility of polyisoprene (Figure 11).
According to [29], chloroform and carbon tetrachloride are good solvents of
polyisoprene. Therefore, these substances were selected as co-solvents (Figure 11). The effect
of chloroform was more efficient, probably because of its high polarity. The optimum
concentration of co-solvents was 3.5 wt. %.
The effect of pressure on polyisoprene solubility in supercritical carbon dioxide modified
with 3.5 wt. % of chloroform at 373 K is shown in Figure 12.
As seen in Figure 12, the modification of supercritical CO2 leads to a strong increase of
polyisoprene solubility, compared with pure supercritical CO2 (Figure 10).
Figure 9. Polyisoprene solubility as a function of mass flow rate of supercritical CO2 (T = 373 K and
P = 20 MPa).
Figure 10. Polyisoprene solubility in pure supercritical CO2 as a function of pressure; ♦ T = 343 K;
■ T = 373 K, ▲ T = 393 K.
Figure 11. Polyisoprene solubility in supercritical CO2 modified by chloroform (♦) and carbon
tetrachloride (■), at T = 373 K and P = 30 MPa, as a function of the mass concentration of co-solvent.
Figure 12. Dependence of the polyisoprene solubility in pure SC-CO2 (■) and in SC-CO2 modified with
3.5 wt. % chloroform (♦), at Т = 373 К.
5. HEAT CAPACITY AND ENTHALPY OF MIXING OF

DEACTIVATED COMPOUNDS IN SUPERCRITICAL СO2
Thermophysical properties of polymers, including polyisoprene, one of the substances
deactivating the catalyst, during the hydrogenation of, diene hydrocarbons have been studied
in details [30-35]. The heat capacity of pure polyisoprene was measured by various authors
[30, 31, 34, and 35]; however, the experimental data are limited to a small temperature range
at atmospheric pressure. The effect of pressure has been studied in [35], by calculations from
P-V-T data [33].
The regeneration with supercritical CO2, of the catalyst holding isoprene, is based on the
study of the dissolution of polyisoprene in supercritical CO2. Heat of dissolution of CO2 in
polyisoprene is known only at room temperature [32]. Excess thermodynamic functions,
including enthalpy of dissolution, can be obtained from data on phase equilibria [36-38], or
calculated from state equations [39-41], however, the derivation of P-V-T data leads to a
significant departure from experimental calorimetric measurements. The accuracy of the
calculations of redundant functions on different models can be confirmed by associating them
with direct measurements of these functions. Later in this section, the results of measurements
of thermal effects, which arise during polymer (polyisoprene) processing with supercritical
carbon dioxide, are reported.
Measurements of the enthalpy of mixing are primarily focused on gas-liquid systems,
SCF-liquid such as СО2-Н2О [26], Н2S-Н2О [42], CO2-methyl diethanolamine aqueous
solutions [43]. Experimental studies of the enthalpy of mixing in gas-solid are reported in
[44], wherein the results of measurements of the enthalpy of mixing of caffeine and cellulose
in CO2 are given. For the system of (polyisoprene-supercritical carbon dioxide) which is
considered here, the heat of solution is known only at room temperature and is about 12.5
kJ/mol [32].
The results of measurements of heat capacity of polyisoprene in the temperature range
from T = 323 K to 473 K are shown in Figure 13, and the enthalpy of mixing of a mixture of
polyisoprene - supercritical CO2 in Figure14.
Figure 13. Variation of the heat capacity of polyisoprene as a function of temperature: (1) - this work;
(2) - [31]; (3) - [30].
Figure 14. Variation of the heat of dissolution of polyisoprene in supercritical CO2 as a function of
pressure, at different temperatures from 323 K to 363K.
All these studies show different behaviors of the variation of the heat capacity and the
heat of dissolution of polyisoprene in supercritical carbon dioxide.
As can be seen in Figure 13, Ср values obtained in this work are consistent within the
error bar with the literature data [30, 31]. At the same time, these data are limited to a
maximum temperature of 360 K. As the temperature rises over 390 K, there is a slight
reduction of heat capacity in the narrow temperature range of 390 to 400 K, apparently
associated with structural changes [44]. The heat capacity measurements are limited to a
temperature of 473 K, due to the degradation of polyisoprene at higher temperature (T = 596
K) [32]. The greatest variations in enthalpy (Figure 14), with the temperature change, occur in
the pressure range of 6 to 15 MPa, along two isotherms T = 323 K and T = 343 K. The
derivative  P T decreases with increasing temperature.
Thus one can say that in the temperature range of 323 to 363 K and the pressure range
from 7 to 22 MPa, the value of polyisoprene heat of dissolution in supercritical CO2 is
negligible, and that dissolution occurs only with absorption of heat.
6. REGENERATION OF LD-265 PALLADIUM CATALYST USED IN

THE PROCESS OF HYDROGENATION OF DIENE HYDROCARBONS
BY SUPERCRITICAL FLUID CO2 EXTRACTION
The catalyst was regenerated using pure supercritical carbon dioxide, at temperatures of
343 K and 423 K and pressures of 10, 20 and 30 MPa.
As seen in Figure 15, there is a decrease in the initial mass of the catalyst, which
corroborates a highest possibility of catalyst regeneration by SCFE method. A greater effect
can be obtained by changing the process parameters or modifying the nature of the extractant.
Solubility of non-polar carbon dioxide can be increased by adding polar co-solvents. The
introduction of a co-solvent increases the yield of the extract and contributes to an extraction
process under milder conditions. It is known that pure supercritical carbon dioxide dissolves
poorly polar compounds, whereas its solubility increases significantly by adding a polar
modifier. Based on previous studies, the effect of different co-solvents on the variation of
mass of catalyst, in regeneration process was studied. Ethanol and dimethyl sulfoxide
(DMSO) were chosen as co-solvents, which, as indicated in [45] are the most effective in the
regeneration of hydrogenation catalysts. The concentration of co-solvents varied in the range
from 0 to 9 wt. %. The results of studies of the effect of the concentrations of various co-
solvents on the change in mass of catalyst during regeneration at T = 423 K and P = 20 MPa
are shown in Figure 16. The graphs show that in the beginning, with the increase in co-
solvent concentration, the change in catalyst mass increases, passes through maximum and
thereafter decreases, and the regeneration efficiency in the case of addition of DMSO
increased 1.5 times. The optimum value of the concentration of the co-solvent to get the best
regeneration is in the range of 5.5 to 6.5%.
For the qualitative determination of deposits on the surface of spent catalysts, the sample
was pre-extracted with chloroform. The resulting extract was evaporated under a stream of
nitrogen and dry residues were analyzed by IR spectroscopy.
Figure 15. Variation of the mass of alumino-palladium catalyst during its regeneration, as a function of
the mass of carbon dioxide; (1) - T = 423 K and P = 30 MPa; (2) - T = 423 K and P = 20 MPa;
(3) - T = 423 K and P = 10 MPa; (4) -T = 343 K and P = 20 MPa.
Figure 16. Variation of the catalyst mass as a function of the concentration of various co-solvents
during regeneration process at T = 423 K and P = 20 MPa; ♦ DMSO; ■ Ethanol.
IR spectroscopic analysis of the dry extracts in chloroform (Figure 17) of the surface of
spent catalysts is represented by the following compounds: styrene oligomers (λ = 756 and
699 cm-1), dicyclopentadiene oligomers (λ = 1339, 1253 and 720 cm-1) and aromatic
hydrocarbons (λ = 1602 and 1493 cm-1) [4].
Figure 17. IR spectra of dry residues of chloroform extracts from the surface of the spent catalyst.
Figure 18. IR spectra of dry chloroform extracts from the surface of catalyst samples: (1) - sample after
the treatment of air-vapor mixture; (2) - sample after SCFE regeneration at 423 K and a pressure
of 20 MPa.
For this catalyst, the region between 1100 cm-1 and 700 cm-1 is of particular interest, and
includes absorption bands of compounds which decrease the activity of the catalyst. Figure
18, shows that the absorption band of dicyclopentadiene oligomers (723 cm-1) remained
unchanged, and absorption bands corresponding to styrene oligomers (749 and 701 cm-1)
disappeared,
For the quantitative determination of the coking of the catalyst, three samples of
deactivated catalysts were studied by thermogravimetry and differential thermal analysis (TG-
DTA), subjected to oxidative regeneration in the factory (sample (1)), regeneration by
supercritical fluid extraction of CO2 (sample (2) and regeneration by supercritical fluid
extraction of CO2 modified by 6 wt. % of DMSO (sample (3)). The measurements were
performed on derivatograph (МОМ, Hungary), under linear heating of the samples (10 K
/min), in air up to 1273 K. Test portions of the catalysts, weighing 450 to 460 mg, were
placed in alumina crucibles; γ-Al2O3 was used as an inert substance.
In the process of Pd/γ-Al2O3 sample heating, progressive decrease in the mass of the
catalyst is observed, which is accompanied by four exothermic reactions. Exothermic
reactions of derivatograms (temperature peaks at 533 K and 613 K), correspond to the
combustion of adsorbed aromatic hydrocarbons (styrene oligomers) [46]. Exothermic
reactions (temperature peaks at 713 K and 873 K), represent the oxidation processes, and the
presence of several effects indicative of heterogeneity, or compaction products, or their
different localization [12].
The maximum loss of weight of sample (1), and therefore the maximum thermal effects
are observed in the temperature range from 333 K to 633 K. The total amount of compaction
products of sample (1) is maximum and reaches 4.9 wt. %, and for sample (2) to 3.3 wt. %.
Reducing the mass loss of the second sample indicates a more efficient removal of
deactivated compounds by SCFE method.
It should also be noted that the regeneration by supercritical CO2, modified with 6 wt. %
of DMSO, leads to reduce the number and the shape of peaks on DTA graphs, and therefore,
to a reduction of the content of compaction products on the catalyst surface.
7. COMPARISON OF THE CHARACTERISTICS OF LD-265 PALLADIUM

CATALYST SAMPLES REGENERATED BY THE CONVENTIONAL
APPROACH AND SUPERCRITICAL CO2 EXTRACTION
The catalyst activity is characterized by its ability to transform raw materials into finished
products, and to some extent, determines the performance of the process. The activity of the
solid catalyst depends not only on the strength of active centers and their quantity, but also
the condition of its surface. The catalyst activity decreases with its operation. The main
reasons for reduction in catalyst activity are the destruction of its structure, or the deactivation
of active centers, that occurs as a result of deposition of coking-like substances formed on
them and in the pores [45].
Four catalyst samples were submitted to the test: original dead catalyst, sample (1),
subjected to oxidative regeneration at a temperature of 723 K, in the factory before the
release, and three samples numbered (2), (3), (4), regenerated with supercritical carbon
dioxide at a pressure of 20 MPa and a temperature of 423 K. Sample (2) corresponds to the
catalyst regenerated by pure supercritical CO2 and samples (3) and (4) were regenerated by
supercritical CO2 modified by 6 wt. % of dimethyl sulfoxide (DMSO) and ethanol,
respectively.
Original BTX fraction and the resulting hydrogenates, from each sample, were analyzed
for hydrocarbon composition, the values of diene and bromine numbers were determined, and
the results are given in Tables 2 and 3.
Table 2. Hydrocarbon composition of BTX fraction before and after hydrotreating

of samples 1 to 4 of LD-265 catalyst
Concentration, wt. %
Test location Column top Reactor outlet Reactor outlet Reactor outlet Reactor outlet
Feed stock
Component before Sample(1) Sample (2) Sample (3) Sample (4)
reactor
Methanol 0.0004 - - -
Ethanol 0.7749 1.726 0.0856 0.6499
Divinyl 0,0008
The amount of C5
hydrocarbons, 2,007 2.263 1.7139 1.7503 1.6667
including:
The amount of
0,0016 0.1149 0.0876 0.0849 0.0998
amylene
Pentane 0,0004 0.0367 0.024 0.0539 0.0372
trace
Isoprene 0,0115
concentration
The amount of
0,0459 0.0027 0.003 0.0013 0.0036
piperylene
Pentadiene 0,0005 - - - -
Cyclopentadiene 1,8505 0.1883 0.1866 0.0975 0.1262
Cyclopentane 0,0383 0.754 0.672 1.095 0.8415
Cyclopentene 0,0583 0.8181 0.7033 0.4165 0.5584
The amount of C6
non-aromatic
5,4735 2.5002 2.9551 3.7656 3.588
hydrocarbons,
including:
Hexane 0,45 0.5615 0.5076 0.6025 0.5532
Hexene + hexadiene 0,013 0.0235 0.0285 0.0554 0.0574
The amount of
0,1729 0.1159 0.4425 0.2452 0.4427
hexene isomers
The amount of
0,4202 0.2485 0.29 0.2191 0.2647
hexadiene isomers
The amount of
methyl-CPD 3,3161 0.5571 0.5486 0.2952 0.4181
hydrocarbons
Methylcyclopentane 0,5296 0.681 0.5334 1.033 0.7677
Cyclohexane 0,1508 0.2484 0.2216 0.3482 0.2803
The amount of C7
hydrocarbons, 1,9683 1.9698 2.099 1.4034 1.1334
including:
Heptane 0,2307 0.3073 0.2977 0.3224 0.3124
The amount of
0,0391 -
heptadiene isomers
Methylcyclohexane 0,2176 0.2254 0.2296 - 0.2293
Concentration, wt. %
Test location Column top Reactor outlet Reactor outlet Reactor outlet Reactor outlet
The amount of
С7Н10+С7Н12 1,3827 1.3486 0.1745 - -
hydrocarbons
The amount of
0,0982 0.0885 0.1267 - -
С7Н14 hydrocarbons
The amount of C8
hydrocarbons, 0,2709 0.5913 0.5764 0.9864 1.2284
including:
Octane 0,0842 0.1079 0.1376 0.0888 0.438
Octene 0,0093 - - - -
The amount of
0,1774 0.4834 0.4388 0.8976 0.7904
С8Н10+С8Н12
С8Н14+ С8Н16
hydrocarbons
The amount of C9
and higher
0,3847 0.269 0.4622 0.7402 0.1352
hydrocarbons,
including:
The amount of
0,1198 0.2038 0.4622 - -
С9Н10 hydrocarbons
The amount of C10
0,0157 - - - -
hydrocarbons
The amount of С11
0,0315 - - - -
hydrocarbons
The amount of
С12Н14+С13Н14 0,0054 - - - -
hydrocarbons
Dicyclopentadiene 0,0333 0.0094 0.0204 0.0118 0.0185
The amount of
aromatic
89,8504 90.5054 89.4263 91.2357 91.5964
hydrocarbons,
including:
Benzene 50,7303 52.4159 50.3222 51.9146 52.1029
Toluene 22,9639 22.6439 22.9901 22.9628 22.9294
Naphthalene 0,0114 0.0072 0.02 0.022 0.0039
The amount of
6,7341 6.3916 6.6969 6.6322 6.5485
xylene
Styrene 7,5655 2.5418 2.4804 1.4561 2.0353
Ethylbenzene 1,7694 6.505 6.6111 7.9995 7.2103
Isopropylbenzene 0,0176 - 0.0147 - -
Methylstyrene 0,0115 - 0.0308 0.0125 0.0119
Sum of С9Н12
and higher 0,0467 - 0.2556 0.236 0.3771
hydrocarbons
The amount of non-
identifiable 0,0424 1.2008 2.7671 0.0328 0.0205
components:
TOTAL: 100 100 100 100 100
Table 3. Comparative analysis of BTX fractions obtained after hydrotreating of samples

1 to 4 of LD-265 catalyst
Methyl
Diene number, Bromine number, Styrene,
Parameter name cyclopentadiene,
g J2/100 g. g Br2/100 g wt. %
wt. %
Spent catalyst LD-265 subjected to oxidative regeneration at 723 K, sample (1)
Feedstock 18.3 32.3 7.57 3.21
Hydrogenation product 2.85 20.5 2.6 0.56
Difference in value 15.45 11.8 4.97 2.65
Conversion, % - - 65.7 82.6
Spent catalyst LD-265 subjected to SCFE regeneration by pure supercritical СО2, sample (2)
Feed stock 18.3 32.3 7.57 3.21
Value difference 15.9 13.3 5.09 2.66
Conversion, % - - 67.2 82.9
Spent catalyst LD-265 subjected to regeneration by supercritical СО2 modified by 6 wt. % of
dimethyl sulfoxide, sample (3)
Feed stock 18.3 32.3 7.57 3.21
Conversion, % - - 80.8 88.8
Spent catalyst LD-265 subjected to regeneration by supercritical СО2 modified by 6 wt. % of
ethanol, sample (4)
Feed stock 18.3 32.3 7.57 3.21
Conversion, % - - 77.5 87.5
The catalytic activity of the catalyst samples was evaluated by the residual value of diene
number in the hydrogenation product. Diene number of original BTX fraction and
hydrogenation products was determined according to the measurement procedure n°417 of
scientific and technological center of Nizhnekamskneftekhim JSC [47]. The procedure is
based on the reaction of diene synthesis (Diels-Alder reaction), by joining the maleic
anhydride to the conjugated double bonds (diene component), in toluene at reflux, in the
presence of a catalyst - iodine, the hydrolysis of the unreacted anhydride, followed by
extraction and titration of the resulting maleic acid, with a sodium hydroxide solution, in the
presence of phenolphthalein.
Diene number of the test sample was calculated as follows:
(Vk  V p )  C  K 127 100

Х ,
mпр 100
(3)
where:
X: diene number, J2g /100 g of the sample;
Vк, Vр: volumes of alkaline solution subjected to control titration and on work
experiment, respectively, cm3;
C: molar concentration of alkaline solution, mol/dm3;
K: correction factor to the concentration of alkaline solution;

127: molar mass of equivalent iodine, g/mol;
mnp: mass of the sample taken for analysis, g; (when the samples are selected for analysis
by volume, the sample mass is V·ρ, where V is the volume of the sample taken for analysis, in
cm3, ρ is the density of the sample at 293 K, in g/cm3).
In addition, for the confirmation of the catalytic activity, the bromine number and the
conversion of two components: styrene and methylcyclopentadiene are further defined in
hydrogenated product. Bromine number of the original BTX fraction and the hydrogenation
products were determined by the measurement procedure N° 373 of scientific and
technological center of Nizhnekamskneftekhim JSC [48]. This procedure corresponds to the
reaction of olefinic compounds with an excess of a standard solution of potassium bromide-
bromate, with molar concentration equivalent to 0.5 mol/dm3 (0.5 N), in the presence of cold
acetic acid at room temperature; the recovery of excess bromine by potassium iodide and
titration of the released of free iodine with a standard solution of sodium thiosulfate, with a
molar concentration equivalent to 0.1 mol/dm3 (0.1 N).
Bromine number with accuracy of up to 0.1 Br, g/100 g of the sample was calculated as
follows:
(V1  N1  V2  N 2 )  7.99 10

A , (4)
W
where:
A: bromine number Br, g/100 g of the sample;
V1: the amount of added standard solution of the bromide-bromate, cm3;
V2: the amount of standard solution of sodium thiosulfate for titration cm3;
N1: the concentration of the bromide-bromate solution, mol/dm3;
N2: the concentration of the sodium thiosulfate solution, mol/dm3;
W: mass of the sample taken for dilution, g;
10: dilution factor;
7.99: conversion factor to Br, g/100 g of sample.
The comparative analysis of the residual value of diene number in hydrogenated BTX
fraction showed that the hydrogenation product obtained on spent catalyst subjected to
oxidative regeneration has diene number of 2.85 J2, g/100 g. Although according to the
requirements [11], the standard is not more than 2 J2, g/100 g, which indicates a relatively low
catalytic activity of the sample (1). The hydrogenation product obtained on the catalyst
subjected to regeneration under pressure of 20 MPa and at a temperature of 423 K, by pure
supercritical CO2 (sample (2)), has diene number of 2.40 J2, g/100 g, also exceeding the
standard value, but with a tendency to increase the catalytic activity as compared with the
sample (1).
As already mentioned, the solubility of polar substances in non-polar carbon dioxide can
be significantly increased by addition of polar co-solvents, as described in [49-50]. In this
regard, studies have been conducted with the catalyst regeneration process using supercritical
CO2 modified with 6 wt. % of dimethyl sulfoxide and ethanol.
Regeneration using modified carbon dioxide allowed to remove polar compounds more
efficiently compared with pure supercritical СО2, which is confirmed, as shown in Table 3.,
by a decrease in the number of diene of hydrogenation products to 1.5 J2, g/100 g and 2 J2,
g/100 g, and bromine numbers to 16.2 Br2, g/100 g and 17 Br2, g/100 g, obtained on samples
(3) and (4), respectively.
The test results showed that sample (3) has a higher catalytic activity as compared to the
rest of samples tested. This is probably due to the fact that DMSO has a higher polarity (4.05
D) in comparison with other substances (chloroform: 1.14 D, methanol: 1.71 D, ethanol: 2.28
D, acetone: 2.71 D) [28], allowing to extract polar compounds in full.
In addition, an increase in styrene and methylcyclopentadiene conversion values is
observed for the catalyst samples subjected to regeneration by SCFE relative to the sample
after the regeneration by oxidation. Thus, the difference in styrene and
methylcyclopentadiene conversion, for samples (1) and (3), was 15.1% and 6.2%.
It has been found that the modification of supercritical СО2, by polar additives, improves
the more complete removal of the coke deposits and increases the catalytic activity of the
catalysts. Thus, the values achieved for the numbers of diene and bromine, as well as the
conversion of styrene and cyclopentadiene to test samples, demonstrate the effectiveness of
the SCFE process, for the extraction of deactivating substances from the surface of alumina
support palladium catalyst.
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Chapter 5
REGENERATION OF DN-3531 AND CRITERION 514

NICKEL-MOLYBDENUM CATALYSTS USED IN
KEROSENE AND GAS OIL HYDROTREATING BY
SUPERCRITICAL CARBON DIOXIDE EXTRACTION
A. A. Jaddoa1,2, T. R. Bilalov1, F. M. Gumerov1,*, F. R. Gabitov1,

Kh. E. Kharlampidi1 and B. T. Burganov1
1
2
University of Technology, Baghdad, Iraq
ABSTRACT
The nature of deactivating deposits formed on the DN-3531 and Criterion 514
nickel-molybdenum catalysts used in the hydrotreating processes of kerosene and gas oil
is analyzed. The solubility of one of these deposits, anthracene, was measured in
supercritical carbon dioxide at temperatures of 308 K and at pressures from 10 to 30 MPa
in association with the researches done previously. The results were described using the
Peng-Robinson equation of state. The regeneration of deactivated catalysts in pure
supercritical carbon dioxide and supercritical carbon dioxide modified with polar additive
was studied in varying process conditions in the temperature range from 323 K to 383 K
and pressures from 10 to 30 MPa. A comparison of the specific surface areas and thermal
analysis of spent and regenerated catalyst samples with supercritical CO2 showed that the
method suggested was very competitive compared to conventional regeneration
techniques.
Keywords: catalyst regeneration, catalyst activity, supercritical carbon dioxide, solubility,

Peng-Robinson equation of state
*
Email: gum@kstu.ru.
110 A. A. Jaddoa, T. R. Bilalov, F. M. Gumerov et al.
1. INTRODUCTION
Hydrocracking and hydrotreating catalysts are important fields of oil refining processes,
which are used to improve the yield of high-quality light oil fractions from heavier crude oil
and petroleum feedstocks containing high levels of impurities.
Hydrocracking is a process used to crack heavy loads in high quality oil, lighter
petroleum products such as vacuum gas oil to diesel, including kerosene and fuels gasoline
engines, in the presence of hydrogen and catalyst, to reduce molecular weight hydrocarbons.
Vladimir Shukhov, a Russian engineer, invented and patented the first thermal cracking
process in 1891 (Russian Empire, patent no. 12926, November 27, 1891). Later, a facility has
been used to a limited extent in Russia.
Hydrotreating (HDT) is an important petroleum refining process, used to remove about
90% of contaminants, such as sulfur, nitrogen, oxygen, metals and saturate and unsaturated
hydrocarbons, from liquid petroleum fractions, to produce fuels that meet the stringent
requirements of product quality and environmental standards. These contaminants, if there are
not removed from the petroleum fractions, may have adverse effects on the equipment, the
catalysts, and the quality of the finished product. Normally, hydrotreating is carried out before
the catalytic cracking process to reduce the sulfur and improve product yields, and to upgrade
the middle-distillate petroleum fractions into finished kerosene, diesel fuel, and heating fuel
oils.
Sulfur is the most abundant element in the oil after carbon and hydrogen. Then the main
hydrotreating reaction is that of desulfurization, but many others are in commensurate with
the severity of the operation.
Hydrodesulfurization (HDS) is a catalytic chemical process widely used to remove sulfur
from natural gas and from refined petroleum products such as gasoline or petrol, jet fuel,
kerosene, diesel fuel, and fuel oils. The sulfur content of crude oil belongs to the following
groups: elemental sulfur; mercaptans, tiols; hydrogen sulfide; sulfides; disulfides, poly
sulfides; thiophenes and derivatives. The hydrodesulfurization process removes the organic
sulfur from petroleum streams by conversion to hydrogen sulfide gas. Sulfur in thioethers and
thiols are the easiest to remove, but sulfur in aromatic rings, such as thiophene, are more
resistant to removal.
The reason for the removal of sulfur is to reduce the sulfur dioxide emissions resulting
from the use of these fuels in motor vehicles, aircraft, railway locomotives, ships, gas or oil
combustion in power plants, residential and industrial furnaces, and other forms of fuel
combustion. Another important objective to remove sulfur from naphtha streams, in an oil
refinery is that the sulfur, even in extremely low concentrations, pollutes the noble metal
catalysts, in catalytic reforming units which are then used to upgrade the octane rating of
naphtha streams.
However, the diminution of sulfur also reduces the lubricating properties of the fuel,
which can lead to accelerated corrosion in the turbine fuel pumps.
In recent years, the clearest change in the oil refining and petrochemical industries
regards the specifications of fuels, gasoline and diesel, as well as some other petroleum cuts,
which puts great pressure on refiners of various countries, who must adapt their processing
methods to meet these new targets. Due to environmental concerns and the newly legislated
Regeneration of DN-3531 and Criterion 514 Nickel-Molybdenum Catalysts … 111
rules and regulations, to reduce harmful emissions from the combustion of fuel, commercial
diesel must meet lower and lower limits on contaminates, such as sulfur and nitrogen.
The new regulations require virtually complete elimination of sulfur in diesel. For
example, the ultra-low sulfur diesel (ULSD) requirement is typically less than 10 ppm sulfur.
Hydrotreating catalysts have been continuously improved over the last years. Typically
their intrinsic activity was increased by a factor of four over the last two decades. The
catalysts have become increasingly sophisticated and one indirect consequence is that they
need more careful procedures for regeneration than in the past.
Another change in petrochemical industries comes from a greater need for productivity
and economic improvements. This leads to manage refining and petrochemical units
differently.
The choice of catalysts depends on the feedstock to be treated and the desired product.
Most of the time, the system is optimized using two or more catalysts with different acid and
hydrogenation functions. Cobalt and molybdenum on alumina support are generally used for
sulfur removal, as they are highly selective, easy to regenerate, and more tolerant to poisoning
agents.
Since nitrogen is usually more difficult to remove from the feedstocks as sulfur, for
removal of nitrogen, catalysts composed of nickel-molybdenum on alumina supports are more
efficient than cobalt-molybdenum, because they have a higher hydrogenation activity,
resulting in the same operating conditions, in a greater saturation of aromatic rings.
In this study, we use a nickel-molybdenum catalyst supported on the alumina substrate.
Thus, hydrotreating processes are carried out with nickel-molybdenum catalyst, “Criterion
514” for kerosene hydrotreating and “DN3531” for gasoil hydrotreating.
Most catalysts used in the refining or petrochemical applications deactivate more or less
quickly with time. It is generally accepted that there are three causes of catalyst deactivation,
the most important being the coke formation. Coke is the term used for these large molecules
often containing polyaromatic rings and which partially covers the active sites, with the risk
of clogging the pores of the catalyst.
The second cause may be damage to active phase structure and dispersion, while the third
one is a contamination by various chemicals which adsorb on active sites. In addition, the
decrease of the partial pressure of hydrogen, in the circulating gas, tightens the process
conditions and facilitates the carbonization of the catalyst.
Deactivating catalyst replacement represents a major cost in petroleum refining. Equally
important are the costs and potential liabilities related to the treatment and disposal of spent
catalysts.
To recover its lost activity, the catalyst can be regenerated in-situ. Until the mid-1970s,
all regenerations of hydroprocessing catalysts have been made in-situ in the unit reactors. In
the regeneration process, the deposits of coke and sulfur on the catalyst are burned with a
dilute stream of nitrogen-oxygen mixture. This is followed by the reduction of some of the
compounds formed during the oxidation step, in a dilute hydrogen stream. The oxidation
reactions are highly exothermic, and they may yield to a loss of catalyst activity or structural
damage to the catalyst and the reactor.
Ex- situ regeneration has gradually become the norm in the world of industry. This
technique is preferable to the in-situ regeneration for many reasons; including the problems of
corrosion, safety, better recover activity, time considerations, because it took too much
downtime without production. In addition, the higher degrees of sophistication of the most
recent catalysts, whether in the field of hydrotreating or hydrocracking, encourage even more
the off-site regeneration.
The samples of spent catalyst regeneration that took place in the framework of this study
were provided by the refinery “Taif-NK”of Nizhnekamsk (Tatarstan).
An alternative to the in-situ regeneration method of the catalyst described above may be
ex-situ regeneration by supercritical fluid, which will be treated in this study. In order to
perform the catalyst regeneration, the solubility of pollutants in supercritical carbon dioxide
was measured. The efficiency of the regeneration was evaluated by surface area
measurements.
Thus, the dependency of the solubility of the catalyst contaminants, in pure supercritical
carbon dioxide and supercritical carbon dioxide with co-solvents such as dimethyl sulfoxide,
was investigated. Anthracene was used as a provisional coke model and its solubility was
measured along isotherms 308.15 K to 323.15 K, as a function of pressure. The experimental
results were described using the Peng-Robinson equation of state.
It is common practice to qualify the performance of HDT catalyst by BET surface area
(SA) measurement. This works rather pretty well so far on alumina based hydrotreating
catalysts. The determination of the surface area is used to evaluate the efficiency of the
regeneration processes. The efficiency of the catalyst regeneration with pure supercritical
carbon dioxide, and supercritical carbon dioxide modified co-solvents, like
dimethylsulphoxide (DMSO), acetone, ethanol, methanol and chloroform, was determined for
various concentrations.
It has been found that the maximum efficiency of the regeneration process corresponds to
a concentration of co-solvent equal to 5 to 6 wt. %, and the highest degree of extraction of
deactivating compounds was obtained with dimethyl sulfoxide as co-solvent.
This clearly shows that regenerated catalysts exhibit excellent performances, not very
different than fresh, and in many cases they can make another cycle with a performance flow
very easily, compensated by an increase of temperature too small to affect the potential cycle
length.
These regenerated catalysts can recover activities rather similar to fresh ones as assessed
by this study.
2. KEROSENE AND GAS OIL HYDROTREATING PROCESS, SPENT

CATALYST CHARACTERISTICS AND DESCRIPTION OF
THE TRADITIONAL WAY OF ITS REGENERATION
During the hydrotreating process the crude oil is subjected to a series of hydrogenation
reactions in order to remove undesirable heteroatoms, such as sulfur (hydrodesulfurization
HDS), nitrogen (hydrodenitrogenation, HDN), oxygen (hydrodeoxygenation, HDO), metals
(hydro demetalling, HDN) and saturate and unsaturated hydrocarbons to produce fuels that
meet the stringent requirements of product quality and environmental standards [1].
The main hydrotreating reaction is that of desulfurization, but many others take place to a
degree proportional to the severity of the operation. Sulfur is removed in order to reduce
sulfur dioxide emissions resulting from the use of these fuels in motor vehicles, aircraft,
railway locomotives, ships, gas or oil burning power plants and other forms of fuel
combustion. During the combustion process, most of the sulfur (about 95-98 %) contained in
the diesel fuel is oxidized to sulfur dioxide, which in the presence of oxygen is oxidized to
SO3, which reacts readily with the water formed in the combustion process to form a sulfuric
acid aerosol. With NOx, it is the major precursor to acid rain. Moreover sulfur and
mercaptans in the raw cuts of crude oil distillation unit can cause corrosion problems in
aircraft engines and fuel storage tanks.
Over the past decade, many countries have imposed a reduction of sulfur level to 10 ppm
fuels, to reduce harmful emissions from the combustion of fuel. In the European Union, the
standard “Euro V,” which specifies a maximum of 10 ppm sulfur in diesel fuel for most road
vehicles, has been applied since 2009. In Russia, the formal technical requirements for fuels
were introduced by Government Decree No. 118, “Technical Regulation on requirements for
automotive and aviation gasoline, diesel and marine fuel, jet fuel and heating oil.” Three
automotive standards cover fuel quality: Type I (Euro 3), Type II (Euro 4) and Type III (Euro
5) with a sulfur content of 350 ppm, 50 ppm and 10 ppm, respectively. Delays in
implementing National Fuel quality standards vary across the country, according to the
refineries, which must complete the necessary upgrades [2]. The quality of diesel fuels in the
US has been specified by ASTM D975, which covered seven qualities diesel fuel oils for
different types of diesel engines. Since 2010, ultra-low sulfur diesel (ULSD) with a sulfur
content of 15 ppm, is the new standard for all on-road diesel fuel. Non-road diesel engine
fuel, like railroad locomotive and marine diesel fuel move also to ULSD in 2014.
The main use of kerosene is an aviation turbine fuel. This product has the most stringent
specifications that must be met to ensure the standards of the different categories of aircraft
safety. The sulfur content of aviation fuel has not been resolved as diesel fuel; specifications
continue to hit highs of 3000 ppm of sulfur, although the average sulfur content worldwide in
jet fuel appears to be considerably lower this limit, between 500 and 1000 ppm. However, the
European Aviation Safety Agency (EASA) and Federal Aviation Administration (FAA)
recently sponsored fuel level studies of ultra-low sulfur jet (15 ppm), to reduce the impacts on
public health [3].
Sulfur is the most abundant element in the oil after carbon and hydrogen. The average
sulfur content varies from 0.03 to 7.89 wt. % in crude oil. The sulfur content of crude oil
belong to the following groups: free elemental sulfur; mercaptans and tiols (R-SH); hydrogen
sulfide; sulfides; disulfides (R-S-S-R'); poly sulfides (R-Sn-R'); thiophenes, and derivatives
thereof, such as benzothiophene and dibenzothiophene.
Only small amounts of nitrogen compounds are found in conventional feedstocks and
there has been no recommended specification for the total nitrogen content in diesel or
kerosene. It is generally acknowledged that the nitrogen compounds cause color stability
problem and gum formation and are responsible for the poisoning of the catalyst in catalytic
hydrotreating processes.
The non-heterocyclic nitrogen compounds which are present in the liquid fuel include
aliphatic amines, anilines and nitriles. Most of heterocyclic nitrogen compounds in crude oil
are unsaturated. Some representative compounds are: pyrrole, pyridine, indole, carbazole,
quinoline, isoquinoline, acridine, pyrrolidine, piperidine and indoline. Nitrogen compounds
such as methyl pyrrole, quinoline or carbazole inhibit the acid catalyst function.
However, with the reduction of crude oil reserves, medium and heavy oil feedstocks
contain higher levels of nitrogen impurities such as carbazole. The combustion of carbazole
releases nitrogen oxides, leading to the formation of acid rain.
In a typical catalytic hydrotreating unit, the feedstock is deaerated and mixed with
hydrogen, preheated in heater, then charged under pressure, through a fixed-bed catalytic
reactor. In the reactor, sulfur, nitrogen and oxygen compounds in the feedstock are converted
into hydrogen sulfide, ammonia and water, in the presence of catalyst. The main process
variables characterizing the hydrotreating process are temperature, the total pressure of the
reactor, the circulation rate of the hydrogen-bearing gas, the feed space velocity, and the
catalyst activity [4, 5]. The space velocity is the ratio between the feed rate into the reactor,
per hour, over the catalyst volume [6]. Increasing the temperature and the partial pressure of
hydrogen increases the sulfur and nitrogen removal and the hydrogen consumption.
Increasing pressure also increases the saturation of hydrogen and reduced the formation of
coke [7].
The increase in space velocity reduces the conversion of the hydrogen consumption, and
the formation of coke [6]. Although increasing temperature improves the removal of sulfur
and nitrogen, it is necessary to avoid excessive temperature because of the increased of coke
formation. The rise in pressure in the system causes an increase of the rate of desulfurization
of the feedstock, reduces the formation of coke and increases the life of the catalyst. The
hydrotreating process is carried out at a pressure of 2 to 5 MPa. After reaching the upper limit
of the pressure, increasing the desulfurization rate due to the increase pressure is negligible.
The study of the factors which influence the hydrotreating depth shows that the
hydrogenation is not primarily facilitated by increasing the total pressure in the system, but by
increasing the partial hydrogen pressure with increasing the hydrotreating pressure [6]. The
sulfur content of the hydrogenation compounds increases dramatically with increase in the
partial pressure of hydrogen up to 3 MPa, and very slightly with increasing the hydrogen
partial pressure above 3 MPa.
The residence time of the feedstock in the reactor decreases with increasing space
velocity and vice versa: the vapor of the feedstock and the catalyst contact time increases with
decreasing space velocity, thus deepening the processing speed. However, the amount of
feedstock flowing through the reactor decreases with decreasing space velocity, i.e., leading
to reduced production capacity. Therefore, a maximum permissible space velocity is
determined for each type of feedstock. The space velocity for different volumetric flow rate is
between 1 and 10 h-1. Thermodynamic calculations have showed that hydrogen assisted
hydrogenation reactions may continue until substantial completion. However, the reaction
rate will be extremely low due to the low partial pressure of hydrogen [8].
Accordingly, the hydrotreating process is carried out with an excess of hydrogen. The
process rate increases with increasing the hydrogen content in the raw gas mixture;
nevertheless, a significant increase in the reaction rate in this case occurs only to a certain
limit. Increase in the volume of hydrogen circulation also reduces coke on the catalyst. Gas
flow rate of hydrogen bearing various conditions is accepted within 250-700 Nm3/m3 of liquid
feedstock [9].
The selection of optimum hydrotreating temperature depends on the quality of the
feedstock, the process leading conditions, the loss of catalyst activity over time, and is located
within 613 to 673 K, for the compounds with boiling points within 503 - 633 K, and 573 to
643 K, for the compounds with boiling points within 413-503 K.
The hydrodesulfurization process is a catalytic process, which removes the organic sulfur
from petroleum streams [10] by conversion to hydrogen sulfide gas, following the basic
equations:
Ethanethiol: C2H5SH +H2 → C2H6 + H2S

Mercaptans : RSH + H2  RH + H2S
Sulfides: R2S + 2H2  2RH + H2S
Disulfides R2S2 + 3H2  2RH +2H2S
Thiophenes RC4H3S + 4H2  RC4H9 + H2S
As the sulfur content increases, the hydrogen pressure must also increase. Residence
times need to increase too, which means production is slower and need more energy to
operate in previous conditions.
The desulfurization reactions are exothermic and the heat of reaction ranges
approximately from 2300 to 2400 kJ/m3 of hydrogen [11]. On the other hand, sulfur can
amalgamate with the nickel content in many metal alloys to form a eutectic alloy with low
melting point, which can increase the lubricity. The process used to reduce the sulfur also
reduces the lubricating properties of the fuel which can lead to accelerated corrosion in
turbine fuel pumps.
The refining process that removes the sulfur also reduces the content of aromatic
compounds and density of the fuel, resulting in a slight decrease in the energy content of
about 1%. This reduction in energy content may slightly reduce peak power and fuel
economy. However the reduction of aromatic content of diesel fuels is also relevant, because
the aromatic hydrocarbons have low cetane number, contributing to the increase of vehicle
emission (primarily the hydrocarbon and particulate matter).
The ease of desulfurization depends on the type of compounds. Sulfur in acyclic aliphatic
sulfides (thioethers) and cyclic sulfides (thiols) are the easiest to remove [12]. On the other
hand, sulfur in aromatic rings, such as thiophene and its benzologs for example:
benzothiophene, dibenzothiophene and benzonaphthothiophene are more resistant to removal
sulfur by hydrodesulfurization [11, 13-14].
Sulfides are the easiest to be hydrogenated (up to 95%); a degree of thiophenes
hydrogenation is 40-50%. Hydrodesulphurization rate decreases with the increase of
molecular weight of petroleum fractions.
The light straight-run fractions, gasoline and kerosene fractions are treated much easier
than gas oil, which is characterized by a higher molecular weight and content sulfur
compounds close to thiophenes.
During the denitrification of feedstocks, nitrogen is removed to form ammonia and
hydrocarbons, following the basic equations:
Pyrrole: C4H4NH + 4H2  C4H10 + NH3

Pyridine: C5H5N + 5H2  C5H12 + NH3
Carbazole: C12H9N + 2H2 → C12H10 + NH3
Quinoline: C9H7N + 4H2 → C6H5C3H7 + NH3
Indole: C8H7N +3H2 → C6H5C2H5 + NH3
Ammonia is later removed from the reactor effluent, leaving only the hydrocarbons in the
product. The heat of reaction of the denitrification reactions is about 2600-2800 kJ/m3 of
consumed hydrogen, but the amount of nitrogen in the feed is generally very small, on the
order of a few parts per million, and therefore its contribution to overall heat of reaction is
negligible [11].
The hydrogenation of unsaturated molecules depends on the nature of the molecules in
the feedstock. In the hydrogenation of an alkene two hydrogen atoms are added to the double
bond of alkene, resulting in a more stable saturated alkane. The relative speed and depth of
the reaction behavior depends on the process conditions, the physicochemical properties of
the feedstock, the catalyst used and its conditioning [2]. This is an exothermic reaction; the
heat of reaction is about 5200 kJ/m3 of hydrogen consumed. The content of alkene is
generally small for straight-run products, but for feeds derived from secondary thermal
processes such as cocking, visbreaking, or resid hydrocracking (H-OIL process or delayed
cocking), it can contribute to a large amount of heat liberated in the hydrocracker reactor.
RCH2CH=CH2 + H2 → RCH2CH2CH3
Alkene Paraffin
In the feed, a fraction of the aromatics are saturated by forming naphthenes. The
saturation of aromatics compounds are a significant part of both the hydrogen consumption
and the total heat of reaction. The heat of reaction varies from 1500 to 3000 kJ/m3 of
hydrogen consumed, depending on the type of structure of aromatic compound. In general
higher reactor pressure and lower temperature produce a greater degree of aromatic
saturation.
C6H6+3H2 → C6H12
Benzene Cyclohexane
The feed of a hydrocracker unit is typically low-quality heavy gas oil, from atmospheric
or vacuum distillation tower, fluid catalytic cracker or coking units. Hydrocracking of large
molecules into smaller molecules occurs in almost all processes carried out in the presence of
excess hydrogen. These reactions release about 1850 kJ/m3 of hydrogen consumed. The
release of heat from hydrocracking reactions contributes significantly to the total heat
liberated in the reactor.
Cracking reactions involving heavy hydrocarbon molecules contribute to the lowering of
the density and formation of smaller alkanes used for fuels (e.g., petrol or diesel) and alkenes
which are used to make polymers or plastics with other important compounds.
An example of hydrocracking reaction is:
RCH2CH2CH2CH3 + H2 → RCH3 + CH3CH2CH3
The feed properties have little direct effect on light product yield, but they affect the
catalyst temperature required to achieve the desired conversion. The yield of light gases (C4-)
and naphta boiling range material is increased when the catalyst temperature is increased to
compensate for a decrease in catalyst activity at the end of running conditions.
The catalyst accelerates the rate at which the sulfur removal reaction occurs. The catalyst
consists of two parts, the catalyst support and the active elements.
The support consists of a solid material with a high porosity that is able of withstanding
the temperature, pressure and adapted to the environmental conditions in the HDS reactor.
The active elements are the metals deposited on the support in form of oxides. Before use, the
catalyst is sulfided in order to regulate activity. Metals in the form of sulfides favor the
desulfurization and denitrification of olefins and mono and polyaromatics.
The support used of the HDS catalyst, is alumina in the form of pellets or extrudates. The
particle size and pore geometry have an important influence on the distribution of reagents.
By reducing the size of the catalyst particles, the desulfurization rate increases, but the
difference in pressure across the catalyst bed decreases and then a balance must be achieved
between the rate of reaction and the pressure drop through the bed. The pore size of the
support should be adjusted around a particular diameter.
Thus for the reactions that take place in the hydrotreatment of gas oils (473-840 K) a
minimum pore size is required to take into account the dispersion restrictions. However, if the
pore diameter becomes too large, the specific surface area decreases (at constant volume),
leading to a diminution of activity.
The choice of catalysts depends on the feedstock to be treated and the product required.
Most of the time, the system is optimized by using two or more catalysts with different acid
and hydrogenation functions. The reactor may also contain a small amount, up to 10 % of
desulfurization and denitrification catalyst in the last reactor bed.
Catalyst activity is determined by the target reaction of components conversion rate. The
higher activity of the catalyst, the higher space velocity of the process must be carried out to
reach a great desulfurization depth.
Cobalt and molybdenum dispersed in a thin layer within the pore system of the alumina
support are today generally used for the removal of sulfur, as they have proven to be very
selective, easy to regenerate, and more tolerant of poisoning agents.
Since nitrogen is usually more difficult to remove from the feedstocks as sulfur, for
removal of nitrogen, catalysts composed of nickel-molybdenum on alumina supports are more
efficient than cobalt-molybdenum, because they have a higher hydrogenation activity,
resulting in the same operating conditions, in a larger saturation of aromatic rings [15]. The
nickel-molybdenum catalyst is useful for the hydrodesulfuration of catalytic cracking
feedstocks, when maximum hydrogen consumption is required.
Another catalyst which has received attention is the nickel-tungsten on alumina, which
exhibits high activity in hydrocracking reactions, and is more effective in removing nitrogen
from aromatic rings, but it is much more expensive than nickel-molybdenum and is therefore
rarely used in fuels refineries.
The degree of hydrodealkylation, hydrocyclization, hydroisomerization and
hydrocracking reactions are controlled by the ratio of alumina to silica of the catalyst support.
In this study, we test the use of a nickel-molybdenum catalyst supported on the alumina
substrate [16]. Thus, hydrotreating processes are carried out with nickel-molybdenum
catalyst, “Criterion 514” for kerosene hydrotreating and “DN3531” for gasoil hydrotreating
that provides protection to catalysts from feed metal contaminants, both catalysts are
manufactured by “Criterion Catalyst and Technology.” The main characteristics of these
catalysts are shown in Table 1.
In the catalyst production process, molybdenum and nickel are deposited on the alumina
support under their oxide form. To make them more selective and active, they need to be
presulfided.
Table 1. Characteristics of Dn-3531 and Criterion 514 for kerosene and

gasoil hydrotreating [16]
Standard Scope of
Name of catalysts Quality of indicators
values application
Aluminum oxide content, Al2O3, wt. % 89.5 Protective layer
“Criterion 514” of kerosene
Molybdenum oxide content, МоО3, wt. % 8.2
catalyst hydrotreating
NiO oxide content, wt. % 2.3 catalyst
Alumino-silicate basis - Al2O3/SiO2, wt. % 55-75
Molybdenum oxide, MoO3, wt. %, less than 30
Phosphorous pentoxide, P2O5, wt. %, less
10
than
1.3 and 2.5 mm Nickel oxide, Ni, wt. %, Gasoil
sized “DN 3531” 6 hydrotreating
less than
catalyst Iron oxide, Fe2O3, wt. % 1-4 catalyst
Calcium oxide, CaO, wt. % 0-1
Potassium oxide, K2O, wt. % 1-4
Sodium oxide, Na2O, wt. % 1-4
The sulfurization process is a reduction of the oxidized form of the metal (molybdenum,
nickel) on the alumina support by conversion into the metal sulfide. This can be achieved, in
the absence of a feedstock containing sulfur, by reaction of the metal oxide with a sulfur-
containing source as hydrogen sulfide, carbon disulfide, mercaptans or dimethyl sulfide
directly in the hydrogen recycle stream. If the feedstock is present and contains more than 1%
of sulfur, an external source is unnecessary [5].
The temperatures for the sulfurization processes are generally in the range of 530 K to
610 K and a minimum pressure of about 1 MPa are also recommended. Sulfurization catalyst
includes the following chemical reactions:
MoO2 + 2 H2S+ H2  MoS2 + 3 H2O
NiO2 + H2S +H2  NiS + H2O
The sulfiding reaction is highly exothermic, and care must be taken to avoid excessive
temperatures during activation, since the temperatures above 690 K from the hot hydrogen
gas, can reduce a substantial amount of metal oxides and cause permanent catalyst
deactivation [17].
The design of the hydrocracker unit is based on a specific rate of feed conversion and an
explicit catalyst life, usually 2 to 3 years between catalyst regeneration. During the course of
the process, the activity of the catalyst decreases due to deposits of coke and metal, and to
maintain the scheme of the conversion rate, the catalyst temperature should be increased [17].
The catalyst manufacturers specify a maximum temperature called the end of run
temperature, which means the end of run condition. When this temperature is reached, the
catalyst must be regenerated or discarded.
The hydrotreating catalyst is very sensitive to certain impurities such as nitrogen and
metals. If oxygenated compounds are present in the feed, they can increase the catalyst
deactivation. Trace of organic and inorganic chlorides, mixed with ammonia resulting of
denitrification reactions, form highly corrosive deposits in the heat exchanger and reactor
effluent lines. Metals, especially arsenic, and alkali and alkaline earth deposit in the catalyst
pores reduce catalyst activity. Iron in the feed can be chemically combined with the heavy
hydrocarbon molecule, or it may exist as suspended particulate. It deactivates the catalyst but
also plugs the catalyst interstices such that the excessive pressure drop develops.
Asphaltenes are found in the vacuum gas oil distillates. In addition to causing excessive
poisoning of the catalyst, asphaltenes can be chemically combined with the catalyst to
deactivate the catalyst permanently. A feed distillation end point higher than designed
accelerates catalyst deactivation and requires higher reactor temperatures, thereby decreasing
the life of the catalyst [18].
The temperature of the treatment of the heavy feedstock is higher than that of light
feedstock. It is the most advantageous to conduct the process at the minimum temperature
which does not cause the formation of coke. With increasing temperature, the amount of
sulfur compounds hydrogenated increases, reaching a maximum at a temperature of 693 K.
With further temperature increases, the rate of hydrogenation decreases. It decreases rather
abruptly for unsaturated hydrocarbons because the hydrocracking reaction take place at
elevated temperature, resulting in a reduced yield of liquid products and increased deposition
of coke on the catalyst [7].
The catalyst activity decreases over time due to the increase in the deposition of coke on
the catalyst surface. The decrease of the partial pressure of hydrogen, in the circulating gas,
tightens the process conditions and facilitates the catalyst carbonization [18]. To recover its
lost activity, the catalyst can be regenerated in-situ, biennially periodically. In the
regeneration process, the deposits of coke and sulfur on the catalyst are burned in a controlled
manner with a dilute stream of nitrogen-oxygen mixture, at a pressure of 2.4 to 2.6 MPa and a
temperature in the reactor above 703 K [18].
This is followed by reduction of some of the compounds formed during the oxidation
step, in a dilute hydrogen stream. During the oxidation, some of the sulfur on the catalyst is
converted into sulfates and some metal sulfates, which are formed as the sulfided catalyst is
converted into the oxide form. These metal sulfates may be reduced by exposure to hydrogen
at high pressure, in metal sulfides with liberation of sulfur dioxide. These reactions are highly
exothermic, and they may result in loss of catalyst activity or structural damage to the catalyst
and the reactor.
The catalyst gradually “ages” due to recrystallization and surface structure changes, as
well as due to adsorption of organometallic and other substances on the catalyst surface which
block the active sites. In this case, the catalyst loses its activity and must be replaced with a
new one [19]. An alternative to the process described above may be the regeneration of the
catalyst by the supercritical fluid, which is described in this study. Table 2, shows a
comparison between the conventional method and the supercritical carbon dioxide method of
regeneration of the catalyst [20].
The temperature of regeneration during the extraction with carbon dioxide is more than 5
times lower than the temperature of the conventional approach that is one of the major
advantages in terms of energy consumption. At temperatures below, the catalyst does not
deteriorate due to its “sintering,” which can occur at higher temperatures. The process time is
reduced, and the number of possible regeneration cycles increases. By the way, in the case of
the regeneration process by supercritical carbon dioxide, it is not necessary to use alkaline
water to neutralize the acid exhaust gas.
Table 2. Comparison between traditional and SCF methods of regeneration
Method Traditional regeneration process SCF regeneration process

Extractant Ozone-air mixture СО2 + co-solvent
Temperature 673 - 873 K 323 - 383 K
Pressure 0.8 - 1.5 MPa 20 - 30 МРа
Process life 30 - 50 h 4-7h
Number of regeneration cycles 3-4 ≥6 - 8
3. MATERIALS, EQUIPMENT, AND APPLIED

RESEARCH METHODS
The samples of spent catalyst regeneration that took place in the framework of this study
were provided by the refinery “Taif-NK.” Figure 1, Tables 3 and 4 show the results of
thermal and thermogravimetric studies of samples of the spent catalysts. TG chart shows the
reduction in the mass of the sample, along a solid line (1) starting at 100 %. FGD-mass
change rate (2) is represented by a dash-dot line. The two lines illustrate how quickly the
reduction of the sample mass was going on. Rates have increased significantly in the
temperature range from 303 K to 376 K. The mass reduction rate has subsequently fallen
sharply in the temperature range from 376 K to 593 K, and has risen again in the temperature
range from 593 K to 673 K, and then fell again in the temperature range from 673 K to 788 K,
has risen again in the temperature range from 788 K to 930 K, then dropped to nearly zero,
and increased again at the end. Thus, according to the DSC data (solid line starting at 87), the
following thermal effects were observed: the evaporation of the moisture accompanied by
heat absorption (endothermic effect) occurred in the temperature range from 303 K to 498 K.
This was followed by two exothermic effects in the temperature range from 498 K to 593
K and from 593 K to 823 K, corresponding to substances containing respectively carbon and
sulfur, respectively, deposited on the catalyst, which were burned [8, 19-20].
Table 3. Results of the study of the reduction of mass as a function

of temperature, by the thermogravimetric method (TG-DTG)
Temperature range, K 303-593 593-788 788-1088 1088-1273 303-1273

Maximum effect, K (376) (673) (930) (-)
Change in mass, wt. % 14.79 5.15 6.27 6.15 32.37
(-) no explicit thermal conversion maximum.
Table 4. Results of the study of thermal effects by differential

scanning calorimetry (DSC)
Temperature range, K 303 - 498 498 - 573 603 - 823

Maxima of thermal effects, K 379 (↓) 553 (↑) 660 (↓)
(↓), (↑) - endothermic and exothermic effects respectively.
Figure 1. Thermal analysis of the nickel-molybdenum catalyst, DN-3531, for kerosene hydrotreater:
(1) - rate of sample mass loss (TG); (2) - rate of sample mass loss (FGD); (3) - observed thermal effects
(DSC).
Figure 2. Schematic diagram of the experimental set-up: (1) - СО2 bottle, (2) - valve, (3) - weighing
device, (4) - weighing control panel, (5) - “ТРМ-148” temperature controller and pressure indicator, (6)
- thermo-compressor cell in cooler bath, (7) - heater, (8) - refrigerator (9) - co-solvent cell , (10) -
extraction cell, (11) - heater of extraction cell, (13) - thermal insulation, (12) - thermocouples,
(4 sensors), (14) - test pressure gauge, (15) - vessel for collecting the extract.
No significant exothermic and endothermic effects were observed at higher temperatures.

The total mass loss of the sample represented 32.37% and 14.79% in the temperature range
from 303 K to 593 K.
The catalyst samples were regenerated in the installation shown in Figure 2, according to
the following procedure.
The catalyst of this study, is placed in a metal basket, weighed with scales and introduced
into the extractor, in the path of the fluid phase (extractant).
Operating parameters of the process are set and regeneration process is carried out. Mass
change of the catalyst sample is evaluated by weighing. The amount of carbon dioxide used
for regeneration is also determined by the weight method.
This equipment also allows conducting studies of the dependence of the solubility of
pollutants components of the catalyst, conventionally taken as a model of coke, in pure
supercritical carbon dioxide or supercritical carbon dioxide with co-solvents.
One method to evaluate the efficiency of the regeneration processes is to determine the
surface area of the catalyst samples regenerated in the set-up shown in Figure 3, according to
the method described in [21, 22]. This method is a modification of the gas adsorption
chromatography, wherein the column packing is itself the sample, and the mobile phase is a
known mixture of an appropriated adsorbate and an inert gas.
A known mixture of nitrogen and helium (12% N2 + 88% He) is passed from the gas
cylinder (1) through a filter-drier (3) and is divided into two streams. One stream is sent to the
relative outlet chamber of the thermal conductivity detector (6).The other stream is directed
into a U-shaped tube (10), loaded with a catalyst sample therein, and then flows into the
measuring chamber of the sensor (6).When the U-shaped tube with a catalyst is immersed in
the Dewar vessel (11) with liquid nitrogen, the nitrogen from the feed mixture is absorbed by
the catalyst sample. When the absorption is complete, Dewar vessel was removed, and the
nitrogen desorption begins.
Figure 3. Surface area measuring equipment : (1) - gas cylinder, (2) - valve, (3) - filter drier, (4,8) - fine
adjustment valves, (5,9) - pressure gauge, (6) - thermal conductivity detector, (7) - recording
potentiometer,(10) - U - shaped tube with the sample, (11) - Dewar vessel with liquid nitrogen, (A) -
intermediated outlet chamber, (B) - measuring outlet chamber.
The absorption and desorption of nitrogen is observed on the recording potentiometer (7),
which detects the signal from the thermal conductivity detector (6). The flow rate of the
mixture is regulated by valves (4, 8), and the pressure is measured by pressure gauge (5, 9).
The curves of both adsorption and desorption and the area under either one of these curves is
a measure of the nitrogen adsorbed.
A key parameter required for optimization of catalyst regeneration process by
supercritical fluid is the solubility of the compounds deactivating the catalyst, or substances
conventionally considered as a model thereof.
4. SOLUBILITY OF CATALYST DEACTIVATING COMPOUNDS

IN SC-CO2
The solubility of compounds deactivating the catalyst, or substances conventionally

considered as a model thereof, is a key parameter needed for optimization of supercritical
fluid regeneration process of the catalyst to be tested. In this present study, anthracene
produced, as it is well-known, from coaltar was taken as a conditional coke model. The data
on the solubility of anthracene in pure and modified supercritical carbon dioxide, over
isotherms 313.15 K and 323.15 K, were previously presented in chapter I. In addition, a study
was carried out on the solubility of anthracene in pure supercritical carbon dioxide and
supercritical carbon dioxide modified with dimethyl sulfoxide, at a temperature of T = 308.15
K, and at pressures from 10.0 to 30.0 MPa, with an average carbon dioxide flow rate
of 0.136 g/min.
Table 5. Solubility of anthracene in pure supercritical carbon dioxide
Pressure, Solubility, 10-6 mole fraction

Time, min. Mass of CO2, g Flow, g/min
MPa Measurements Average
8.638
10 600 60 0.1 9.049 9.049
9.46
41.766
15 510 65 0.13 43.665 43.538
45.184
70.55
20 500 70 0.14 74.079 73.136
74.783
82.287
25 500 75 0.15 83.932 83.603
84.591
85.448
30 500 80 0.16 85.756 85.867
86.382
The need for new measurements of the solubility of anthracene in pure SC-CO2, was
considered after looking at the large number of research papers already published on the
subject [23-27], because the reported data show a divergence by more than three times. The
measurements were performed according to the procedure described above, at a temperature
of T = 308.15 K and at pressures from 10 to 30 MPa, our results were compared to literature
data, and they are shown in Figure 4 and Table 5. The solubility data measured in this study
were within the range of previous data reported in the literature, but do not repeat them.
Figure 4. Solubility of anthracene in SC-СО2 at Т = 308.15 K, (1) - [23], (2) - [24], (3) - [25],
(4) - [26], (5) - [27], (6) - this work.
Figure 5. Effect of the flow rate of supercritical carbon dioxide on the solubility of anthracene
at T = 308.15 K and P = 10 MPa.
Indeed, the solubility in research reports [24-25] was investigated in static mode, to
obtain the maximum equilibrium concentration of an analyte in the fluid. The remaining
research papers have implemented the method of dynamic measurement of solubility, but the
gas flow in each case, ranged from 0.5 to 1.5 g/min, which is significantly higher than the
flow rate values in the framework of this research paper. It is likely, that these flow values
which gave lower values of the solubility, do not reach the equilibrium concentration of the
solute in the fluid flow. This is confirmed by further studies conducted on the effect of the
flow rate of supercritical carbon dioxide on the solubility of anthracene, the results are shown
in Figure 5. When the flow rate exceeds 0.3 g/min., the solubility decreases. The study was
conducted at T = 308.15 K and P = 10 MPa.
Table 6. Thermodynamic parameters of the test substances
Anthracene [24] CO2 [25]

Critical temperature Тc, K 869.25 304,2
Critical pressure Рc, Pa 3313300 7386593
Acentric factor w 0.567579 0.225
Vapour pressure Рvp, Pa 0.00002 -
Binary interaction coefficient mij 0.29
Critical parameters of anthracene are from the article [24] and are presented in Table 6,
which also shows the critical parameters of carbon dioxide [25], the vapor pressure of
anthracene and the binary interaction coefficient of “supercritical carbon dioxide-anthracene”
system at T = 308.15 K.
Figure 6. Variation of the solubility of anthracene in supercritical carbon dioxide as a function of

pressure, (1) - experimental data, (2) - calculation with one binary interaction parameter, (3) calculation
with three binary interaction parameters.
Low accuracy description in this case is due to the lack of experimental data on the vapor
pressure of anthracene at the temperature of the experiment, instead of which the data
calculated using the Lee-Kesler method were adopted providing only approximate values of
this parameter [29].
The description of the results is given in Figure 6. The experimental results were
described using the Peng-Robinson equation of state in accordance with the procedures
described in Chapters I and III, using one and three binary interaction parameters,
respectively. The standard deviation of calculated values amounted to 25.28% and 10.75%,
respectively.
Despite that the model using three binary interaction parameters enables a more accurate
description, and the standard deviation of experimental data from the theoretical curve is
reduced by more than twice. The model with one binary interaction parameter repeats the
experimental solubility values behavior, which is no less important than the accuracy of the
description.
Another important issue is the study of supercritical fluids solubility characteristics
modified by co-solvents. It has been found in previous studies [30-33], that dimethylsulfoxide
(DMSO) in amounts of about 5 wt. % CO2, can significantly improve the efficiency of
regeneration of different types of catalysts. However, no data is present in the literature on the
solubility of anthracene in supercritical carbon dioxide with DMSO as co-solvent. For this
reason, the aptitude of supercritical carbon dioxide containing 5 wt. % of DMSO, to dissolve
anthracene was studied. Measurements were also carried out at T = 308.15 K, in the pressure
range from 10 to 30 MPa. The results of these investigations are shown in Figure 7, and Table
7. The data show that the use of dimethylsulfoxide may significantly enhance the process of
removing pollutants from the catalyst surface.
Table 7. Solubility of anthracene in supercritical carbon dioxide, modified with dimethyl

sulfoxide, at T = 308.15 K
Pressure, Time, CO2 mass, Flow rate, Solubility, 10-6 mole fraction
MPa min. grams g/min Measurements Average
101.341
10 600 60 0.1 102.385 102.501
103.778
119.147
15 510 65 0.13 121.280 121.889
125.241
130.82
20 500 70 0.14 139.721 137.904
143.163
144.981
25 500 75 0.15 150.625 150.796
156.783
156.300
30 500 80 0.16 157.031 157.518
159.225
Figure 7. Solubility of anthracene in (1) - pure carbon dioxide and (2) - carbon dioxide modified with 5
wt. % of DMSO, at T = 308.15 K.
5. REGENERATION OF THE MIXTURES OF DN-3531 AND

CRITERION 514 CATALYSTS USED IN HYDROTREATING OF
KEROSENE AND GAS OIL BY SUPERCRITICAL CO2 EXTRACTION
The process of regeneration of dn-3531 and criterion 514 hydrogenation catalysts has
been studied experimentally in the following manner. To ensure a high level of saturation of
supercritical carbon dioxide with deactivating compounds, the mass flow of СО2 was
calibrated in a preliminary study, in order to investigate the influence of the mass flow rate of
supercritical CO2 on the change in mass of deactivated catalyst (Figure 8).
In the first series of experiments, the catalyst samples were regenerated using pure СО2.
Regeneration process is carried out along isotherms, in the temperature range of 323 K to
383 K, at pressures of P = 20 MPa and 30 MPa (Figure 9). The graph shows that regeneration
process is more efficient at T = 383.15 K and P = 30 MPa. In this case, a decrease 6.9 wt. %,
in the initial mass of the catalyst is observed, indicating a significant potential for
regeneration of the catalyst using the method under discussion.
A greater effect can be obtained by increasing the mass of carbon dioxide used in the
method, the modification of operating parameters of the method and the physical and
chemical nature of the extractant. In the latter case, we consider the change of the extracting
agent and, in addition, the use of a polar additive. The extraction with supercritical fluid, in
the catalyst regeneration process, generally causes no reduction in the mass fraction of the
active component, because the metals are nearly insoluble in the supercritical fluid media
[30].
Figure 8. Changes in the mass of catalyst in relation to the mass flow rate of supercritical carbon
dioxide at T = 383 K and P = 30 MPa.
Figure 9. Change in the mass of nickel-molybdenum catalyst with respect to the mass flow of pure
SC-СО2.
(upper catalyst layers) (lower catalyst layers)
Figure 10. Variation of the mass of catalyst samples as a function of the mass of pure supercritical CO 2
at T = 323 K and P = 20 MPa, following the top and bottom location of the catalyst in the reaction
column.
Following the regeneration process at T = 323.15 K and P = 20 MPa, the reduction of the
mass of catalyst sample at the bottom of the reactor was 5.42 wt. %, while for the sample of
the upper layer, this value was 4.42 wt. % (Figure 10). This is quite typical of the behavior of
bottom feeding of reaction mixtures [10].
It is known that the dissolving capacity of non-polar carbon dioxide compared to polar
substances is limited, which hinders the result in the development of certain technologies
[30]. The dissolving ability and selectivity of the solvent are largely determined by the
saturated vapor pressure of the solute. Adding polar co-solvents often leads to a significant
increase in the solubility. Since the forces of interaction between the co-solvent molecules
and solutes are specific, it often results in improving the selectivity of the extraction process.
Documents [30-33] show that supercritical CO2 without a co-solvent dissolves slightly
polar compounds, whereas the dissolving capacity is greatly increased by the addition of a
co-solvent.
Addition of modifiers such as methanol, ethanol and other in a percentage ratio from
0.1 to 20 wt. % can be achieved before feeding the extractant into the extractor or directly in
the extractor [30].
The comparison of the efficiency of the catalyst regeneration with pure supercritical
carbon dioxide, and modified acetone, is illustrated in Figure 11. This figure shows that the
addition of a co-solvent has significantly increased the capacity of SC-СО2 to extract the
poisoning compounds and thus intensify the catalyst regeneration process.
Figure 11. Variation in the mass of catalyst samples in function of the mass of the extraction medium
(pure CO2 and CО2 + acetone) used in the regeneration process, (Т = 383 K, Р = 30 МPа).
The addition of polar co-solvent to carbon dioxide increased the capacity to remove polar
compounds included in the coke. However, it was necessary to determine the optimal
physical and chemical nature of co-solvent, as well as the optimal concentration of polar
additive in order to improve the result [30].
As in the case with the flow of supercritical fluid solvent, different concentrations of
co-solvent define different efficiencies of regeneration (Table 8, Figure 12).
Therefore, the catalyst regeneration process using supercritical carbon dioxide modified
with the following polar additives: dimethylsulphoxide (DMSO), acetone, ethanol, methanol
and chloroform, was carried out under a second set of experiments.
First we find that the mass of the catalyst increases with the concentration of co-solvent
and goes to a plateau, and then decreases.
The maximum efficiency of the regeneration process corresponds to a co-solvent
concentration equal to 5 to 6 wt. %. Subsequent experiments on the regeneration of catalyst
samples are conducted with this value of the concentration of co-solvent (5%). The results of
these studies are shown in Figures 12 and 13.
Table 8. Effect of the solvent concentration on the catalyst performance of

the regeneration process
Mass of solvent Changes in the

СО2, g Dimethyl sulfoxide, g sample mass
Experiment – 1 - 1340 15.72 (≈1%) 5.415
Experiment – 2 - 1320 30.12 (≈2%) 6.615
Experiment – 3 - 1300 67.5 (≈5%) 8.615
Experiment – 4 - 1350 150 (≈11%) 8.165
СО2, g Acetone, g sample mass
Experiment – 1 - 1340 15.72 (≈1%) 4.95
Experiment – 2 - 1320 30.12 (≈2%) 6.115
Experiment – 3 - 1300 67.5 (≈5%) 8.115
Experiment – 4 - 1350 150 (≈11%) 7.665
СО2, g Ethanol, g sample mass
Experiment – 1 - 1340 15.72 (≈1%) 4.415
Experiment – 2 - 1320 30.12 (≈2%) 5.615
Experiment – 3 - 1300 67.5 (≈5%) 7.615
Experiment – 4 - 1350 150 (≈11%) 7.165
СО2, g Methanol, g sample mass
Experiment – 1 - 1340 15.72 (≈1%) 3.915
Experiment – 2 - 1320 30.12 (≈2%) 5.115
Experiment – 3 - 1300 67.5 (≈5%) 7.115
Experiment – 4 - 1350 150 (≈11%) 6.665
СО2, g Chloroform, g sample mass
Experiment – 1 - 1340 15.72 (≈1%) 3.415
Experiment – 2 - 1320 30.12 (≈2%) 4.615
Experiment – 3 - 1300 67.5 (≈5%) 6.615
Experiment – 4 - 1350 150 (≈11%) 6.165
As can be seen in Figure 12, the highest degree of extraction of deactivating compounds
is obtained using dimethyl sulfoxide as a co-solvent. This solvent has a higher polarity (4.05
D) in comparison with other substances (chloroform: 1.14 D, methanol: 1.71 D, ethanol: 2.28
D, acetone: 2.71 D) [34], that allows a more complete extraction of polar compounds.
Figure 12. Change in the mass of catalyst samples in the extraction process of regeneration by
supercritical carbon dioxide (T = 363 К, P = 25 MPa), as a function of the concentration of various co-
solvents.
Figure 13. Change in the mass of catalyst samples in the regeneration process of extraction by
supercritical carbon dioxide with different co-solvents, at an optimal concentration of 5 wt. %,
at T = 383 К, and P = 30 MPa in terms of the mass of carbon dioxide modified.
6. COMPARISON OF THE CHARACTERISTICS OF DN-3531 AND

CRITERION 514 CATALYST SAMPLES REGENERATED BY
CONVENTIONAL AND SUPERCRITICAL CO2 EXTRACTION
One of the main indicators characterizing the catalyst is its specific surface area [1].
According to the method of determining the specific surface area described above, this
parameter was determined for the following samples:
Pure alumina calcined for 3 hours at a temperature of 773 K;
1. A non-regenerated spent catalysts sample;

2. A catalyst sample regenerated according to conventional techniques of coke burning
during 2 hours, at a temperature of 823 K;
3. A catalyst sample regenerated with a mixture of SC-СО2 and dimethyl sulfoxide
at T =363.15 K and P= 25 MPa.
The results of this study are shown in different chromatograms (Figures 14 to 17) and
Table 9.
The specific surface area (m2/g) is calculated by multiplying the scale, the peak height
(mm), the peak width (mm) given in Table 9, and the constant value of 0.0005385 for Al2O3,
and dividing the result by the volume of gas (cm3).
Catalyst sample regenerated with supercritical carbon dioxide modified with dimethyl
sulfoxide, has a specific surface area close to that of the pure aluminum oxide, which is not
the case of the sample regenerated in air flow at 823 K.
Thus, the whole regeneration, and therefore the effectiveness of the supercritical fluid
approach, is significantly higher than in the conventional high temperature process.
Table 9. Determination of the specific surface area of various catalyst samples
Peak Peak Specific

Peak Volume of
Sample Scale height width surface area,
area, (mm2) gas (cm3)
(mm) (mm) (m2/g)
Pure alumina 1:64 123 4.2 337920 0.105 182.0
Spent catalyst 1:32 159 4.8 201506 0.101 108.5
Air regeneration 1:64 100 3.5 217475 0.103 117.1
Regeneration with
SC - CО2 + 1:64 124 4.2 317440 0.105 170.9
dimethylsulfoxide
Figure 14. Chromatograms of nitrogen desorption from pure Al2O3 samples calcined for 3 hours
at 773 K.
Figure 15. Chromatograms of nitrogen desorption from the spent catalyst.
Figure 16. Chromatograms of nitrogen desorption from the sample regenerated with air for 2 hours
at 823 K.
Figure 17. Chromatograms of nitrogen desorption from the sample regenerated with a mixture of
SC-СО2 and dimethyl sulfoxide at T =363.15 K and P = 25 MPa.
To assess the quality of regenerated samples, a differential thermogravimetric analysis of

the catalyst samples was carried out, and compared to the initial sample for which the results
are shown in Figure 1.
Figure 18 to Figure 22, show the results of the thermogravimetric analysis of catalyst
samples regenerated in supercritical carbon dioxide modified by polar additives.
The method of analysis of catalyst samples is an integrated differential thermal analysis
(TG-DTG, DSC) performed with a STA 409PC Luxx brand synchronous thermal analyzer.
The analysis is performed in the temperature range of 303-1273 K, at a heating rate of
10 K/min, with lidded platinum crucibles and air as a medium carrier.
The comparison of the figures presented above with the data obtained for the spent
catalyst (Figure 1) shows the reduction of the amount of pollutants, from the sample 5 to the
sample 1, as it is evidenced by the reduction progressive of the height of the peaks of line 3
(observed thermal effects). The height and width of peaks in the graphs indicates the large
amount of the pollutant, while decreasing their size indicates their removal during the
regeneration process. The analysis showed that the regeneration process has progressed most
successful when adding dimethyl sulfoxide to the supercritical carbon dioxide (see
Figure 17).
Table 10. Results of the thermogravimetric (TG-DTG) method
Sample
Mass loss in wt. % (maximum effect, K).
number
Temperature range 303-443 K 443-618 K 618-773 K 773-1118 K 303-1273 K
1 10.23 (376 K) 13.91 (263 K) 4.92 (680 K) 6.41 (928 K) 40.35
Temperature range 303-593 K 593-773 K 773-1073 K 303-1273 K
2 15.10 (383 K) 4.51 (661 K) 7.07 (932 K) 34.16
3 14.80 (378 K) 4.37 (666 K) 7.15 (933 K) 33.96
4 14.15 (373 K) 4.46 (658 K) 7.62 (935 K) 33.97
5 14.17 (380 K) 4.92 (669 K) 6.90 (926 K) 33.22
Table 11. Results of the study of thermal effects by the differential scanning
calorimetry method (DSC)
Characteristics (maxima) of thermal effects, K

Sample No.
303-498 K 498-598 K 598-773 K
1 385 (↓) 573 (↑) -
2 383 (↓) 553 (↑) 659 (↑)
3 380 (↓) 550 (↑) 659 (↑)
4 379 (↓) 546 (↑) 658 (↑)
5 381 (↓) 554 (↑) 659 (↑)
(↓), (↑) are endothermic and exothermic effects, respectively.
Figure 18. Thermal analysis results for the catalyst regenerated in supercritical carbon dioxide with
dimethyl sulfoxide as co-solvent, (1) - mass loss of the sample (TG); (2) - mass loss rate of the sample
(FGD); (3) - observed thermal effects (DSC).
Figure 19. Thermal analysis results for the catalyst regenerated in supercritical carbon dioxide modified
with acetone as co-solvent, (1) - mass loss of the sample (TG); (2) - mass loss rate of the sample (FGD);
(3) -observed thermal effects (DSC).
with ethanol as co-solvent, (1) - mass loss of the sample (TG); (2) - mass loss rate of the sample (FGD);
(3) -observed thermal effects (DSC).
with methanol as co-solvent, (1) - mass loss of the sample (TG); (2) - mass loss rate of the sample
(FGD); (3) -observed thermal effects (DSC).
with chloroform as co-solvent, (1) - mass loss of the sample (TG); (2) - mass loss rate of the sample
(FGD); (3) - observed thermal effects (DSC).
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[11] Parkash S. Refining Process Handbook, Elsevier, 2003.
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[13] Babich I.V, Moulijn J.A. Science and Technology of Novel Processes for Deep
Desulfurization of Oil Refinery Streams. Fuel, 2003, 82: 607-631.
[14] Javadli R., de Klerk A. Desulfurization of Heavy Oil. Appl. Petrochem. Res. 2012, 1:
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[15] Steiner P., Blekkan E.A. Catalytic Hydrodesulfurization of a Light Gas Oil over a NiMo
Catalyst: Kinetics of Selected Sulfur Components. Fuel Processing Technology. 2002,
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Chapter 6
SYNTHESIS OF THE PALLADIUM CATALYST BY

SUPERCRITICAL СO2 IMPREGNATION METHOD
PERFORMED IN STATIC AND DYNAMIC MODES
T. R. Bilalov, A. A. Zakharov, B. T. Burganov,

F. M. Gumerov*, Kh. E. Kharlampidi and G. I. Fedorov
ABSTRACT
The results of the research process on the methods of impregnation using
supercritical CO2 in static and dynamic modes, to synthesize a palladium catalyst are
reported. The kinetics of the process is determined in the pressure range from 15.0 to 35.0
MPa, for temperatures of 308.15 K, 313.15 K, 318.15 K, 323.15 K, 328.15 K and 333.15
K. The results of the working conditions, and the activity measurements of the sample
surface of the catalyst synthesized by impregnation of an aluminum oxide support, with
supercritical carbon dioxide suggests that this approach is competitive with traditional
impregnation methods.
Keywords: supercritical carbon dioxide, aluminum oxide, impregnation, palladium catalyst,

activity
1. INTRODUCTION
Technical progress in many industries, such as chemicals, oil extraction and processing of
oil are closely linked to the use of catalysts. Today, the major challenges of modern industry
are to develop clean and efficient processes, for example in the chemical industry to produce
sulfuric acid, nitric acid and ammonia. Many branches of the national economy are using
*
Corresponding author address: Email: gum@kstu.ru.
142 T. R. Bilalov, A. A. Zakharov, B. T. Burganov et al.
these substances or substances manufactured from them. However, the large scale production
of these products was only possible with the discovery of catalysts for their synthesis and the
development of means of implementation to related processes. For example, nowadays, the
catalysts have gained considerable importance in solving the purification of exhaust gases
from various contaminants.
The catalysts promote an increase in the reaction rate and a temperature decrease in the
conditions of its implementation due to the reduction of the activation energy; as a result of
this, a considerably reduced cost of products and, in general, an improvement of their quality
[1].
Another major challenge associated with the catalysts is the development of energy-
saving technologies and production resources. Nowadays, catalysts are mainly manufactured
using wet-chemical techniques. Wetness impregnation, sol-gel, precipitation, grafting and
solid-state reactions, just to consider some of them, are batch processes, which needed several
subsequent treatments such as filtration, drying and calcinations.
Among these methods for producing deposits on the catalysts, the impregnation is one of
the most developed [1]. Many traditional impregnation methods are known; their
implementations depend on the systems and operating conditions [2].
In particular, the dip method consists to immerse a crystal support in an impregnating
solution, at a certain temperature under stirring conditions. The desired components are then
selectively adsorbed on the support. The disadvantage of this method is a significant loss of
expensive active components in the preparation of catalysts.
When the spray method is used, a carrier is sprayed with a solution of active metal
compounds (e.g., salts). There is no loss of impregnating solution that is particularly
important when expensive components are used. The process is relatively inexpensive,
without left over, but a homogeneous catalyst is difficult to prepare.
Another group of conventional methods for the preparation of deposits on catalysts is the
impregnation of active metals on supports until complete absorption, within an evaporating
solution. This method is used in the production of relatively small amounts of catalyst. The
impregnation is carried out using a slight excess of a solution, which is then evaporated. In
this process there is virtually no waste. Sometimes the deposit of active component in a thin
surface layer when the concentration of the solution increases during evaporation is also
possible. However, this may result in a decrease in the activity of the product and a lower
mechanical strength.
Palladium-metal supported catalyst is widely used in hydrogenation reactions for the
synthesis of fine and bulk chemicals. Their activity and selectivity toward different molecules
are strongly related to the dispersion of the metal active phase and to its interaction with the
support, which becomes an essential parameter in the catalyst preparation.
Processes for the selective hydrogenation of liquid and gaseous fractions of pyrolysis oil
in Russia and abroad are traditionally carried out in the presence of selective palladium
catalysts. In addition to the cost of the metal itself, another key parameter is the metal
loading. The use of non-optimal catalyst performance leads to losses of significant economic
importance, in particular, to the loss of ethylene as a result of a non-selective hydrogenation,
in hydrogenation process of ethane-ethylene fraction [2]. In this regard, the selective
hydrogenation catalysts are constantly updated and improved, including reduced
concentrations of precious metals in catalysts. Modern catalysts in the hydrogenation of
acetylene to ethane - ethylene fraction (EEF) contain 0.01 wt. % to 0.05 wt. % of palladium.
Synthesis of the Palladium Catalyst by Supercritical СO2 Impregnation Method … 143
G83 and G58B catalyst (Sud-Chemie AG, Lenbachplatz 6, Munich, 80333, Germany),
contain 0.015 wt. % and 0.035 wt. % of palladium, respectively.
The production of catalysts has become an independent industry, rapidly developing,
requiring increased energy consumption [3]. In the production of catalysts, the defining
characteristic is not the main cost, but the activity and stability of the catalyst in their work.
The use of supercritical fluids as extractants and solvents in the above processes is one of the
most promising ways to improve the processes of regeneration of spent catalysts and
synthesis of new catalytic systems like was discussed in [4-6]. Thus, if the scope of this
approach to regeneration has been the subject of researches and even commercial
achievement for several decades [7-12], the research on the synthesis of catalysts using
supercritical fluid medium appears only recently in several publications [9, 13-14].
The analysis of the publications of the literature shows the existence of a large number of
precious metal-organic complexes, sufficiently soluble in the supercritical carbon dioxide
[15-16]. For the synthesis of catalysts using supercritical fluid impregnation method, the
following conditions are desirable: a relatively easy formation of the complex, a good
stability and a low decomposition with respect to the temperature.
The results of the research of supercritical fluid CO2 impregnation process performed in
static mode, within the challenge of the synthesis of palladium catalysts are reported. The
kinetics of the process is characterized in the pressure range from 15.0 to 35.0 MPa at the
temperatures of 308.15 K, 313.15 K, 318.15 K, 323.15 K, 328.15 K and 333.15 K.
The palladium chloride benzonitrile complex PdCl2(C6H5CN)2, whose solubility in
SC-CO2 was published previously in the literature [9, 17], and shown in Figure 1, fulfills all
the above mentioned requirements.
Figure 1. Solubility of palladium chloride benzonitrile complex in SC-CO2 at (1) - T = 308.15 K, (2) –
T = 318.15 K and (3) - T = 328.15 K; (4-6) - corresponding theoretical calculations, see ref. [9, 17].
2. SYNTHESIS OF THE PALLADIUM CATALYST BY SUPERCRITICAL

СO2 IMPREGNATION METHOD PERFORMED IN STATIC MODE
2.1. Experiments
The synthesis of a palladium chloride benzonitrile complex is carried out according to the
method described in [16]. For the synthesis, the following materials are used: carbon dioxide
CAS # 124-38-9 with 99.995%, ultra high purity of CO2 (Russian State standard
No. 8050-85, certificate of quality No. 2052, supplier Eco-Farm Ltd., Kazan, Sybyrsky trakt
str, 34); palladium chloride CAS # 7647-10-1, purity of 99.99% (supplier Eco-Farm Ltd.,
Kazan, Sybyrsky trakt str, 34) and benzonitrile, pure for analysis, CAS # 100-47-0 with the
main part of the component not less than 99.7% (supplier Eco-Farm Ltd., Kazan, Sybyrsky
trakt str, 34).
Figure 2. Schematic diagram of impregnation experimental unit: (1) - refrigerator, (2) - pneumatic
pump, (3) - saturating cell with the electric heater and thermal insulation , (4) - separator, (5) -
flowmeter (6), (3a) - impregnation cell with electric heater and thermal insulation (6), (7)- back
pressure regulator, (8) - the model manometer.
Kinetics research on the impregnation process by supercritical carbon dioxide and the
impregnation of aluminum oxide with a benzonitrile palladium chloride complex, was
performed in an experimental test apparatus. The schematic diagram is shown in Figure 2.
The experimental unit mentioned above was realized following the basis of the
supercritical fluid extraction unit R-401, built by Reaction Engineering Inc., (Reaction
Engineering Inc., Munwin-dong, Gwacheon-si Gyeonggido 427-090 Korea).
The test apparatus includes the liquid pump for CO2 supply, with the maximum
efficiency of 100 cm3/min and at a maximum pressure of 40 MPa; two high pressure cells,
used as saturation cell and impregnation cell, with respective volumes of 1.5 and 0.5 dm3, and
also a separator. The temperature control system of the unit provides heating and controls the
temperature of cells up to 373 K. Experimental unit offers possibilities for the recirculation of
carbon dioxide in the closed system “pump saturating cell” and sharp pressure dumping in the
impregnation cell.
The Impregnation Process by Supercritical Fluid CO2 in the Static Mode is Performed
as Follows
The sample of palladium chloride benzonitrile complex is placed in saturating cell, and
the sample of Al2O3, CAS # 1344-28-1, the catalyst carrier (supply by Eco-Farm Ltd., Kazan,
Sybyrsky trakt str, 34) is set up in the impregnation cell. In a first time, within 10 to 20
minutes, the flow of CO2 is recycled only between the pump and the saturating cell, with the
purpose of the saturation of the palladium chloride benzonitrile complex by carbon dioxide
by.
After that, the solution of the palladium chloride benzonitrile complex in supercritical
carbon dioxide, moves to the high pressure impregnation cell, wherein the system:
impregnation solution-impregnated matrix is maintained under supercritical conditions for 15
to 20 minutes, to reach the corresponding equilibrium. After this time, a strong pressure
dumping is made. As a result, the carbon dioxide dissolving ability falls, and the
impregnating material uniformly flows throughout the matrix volume.
The efficiency of the impregnation process is estimated by the weight method of
increasing the mass of the catalyst support sample after completion of the experiment.
2.2. Results and Discussion
Search of optimal parameters for implementing the process involves the experimental
realization of stages of SC-CO2 saturation, with an impregnation material and makes the
impregnation of the solid matrix to a wide variation in the key parameters, such as
temperature and pressure, carbon dioxide flow rate and duration of samples being kept in the
impregnation cell before strong pressure dumping.
Key characteristics of the impregnation process, realized in the temperature range
308.15 K to 333.15 K and pressure of 17.5 MPa, are shown in Table 1. It is worth noting that
the choice of the pressure value is largely fortuitous, rather than intentional or especially
connected with the nature of the change of solubility of a palladium chloride benzonitrile
complex in SC-CO2 (Figure 1). But it is nevertheless important to note that this value was
almost equal to the value of the pressure in the second crossover point, in the discussion of
binary system with regard to the results of SC-CO2 impregnation process, where applicable.
Comments of Table 1:
 At a given temperature, when the flow rate of carbon dioxide, in the recycle system
of the solvent saturated with impregnated material increases, the efficiency of
impregnation processes, with the same duration, falls naturally. Higher flow rates
lead to lower contact time of solvent dissolved in the material system, and a smaller
concentration of palladium chloride benzonitrile complex in carbon dioxide, led to
the impregnation cell. The preferable range of CO2 flow rate is from 1 to 5 cm3/min.
 The results given in Table 1 clearly show the preference of 15 to 20 minutes of
contact time, of the impregnated matrix in SC-CO2 impregnation material solution,
prior to strong decompression. This time in the opinion of other researchers is
sufficient for the diffusion of the supercritical fluid solution throughout the volume
of a porous matrix and is present in the relevant publications [4-6, 8].
Table 1. Increase in the mass of the catalyst support, as a result of SC-CO2

impregnation process, in percent of initial weight (at 17.5 MPa)
Temperature, СО2 flow rate Impregnation time (min)

(K) (cm3/ min) 5 10 15 20
1 0.1493 0.2102 0.2595 0.2732
5 0.1461 0.2058 0.2541 0.2675
308.15 10 0.1152 0.1622 0.2003 0.2108
15 0.0833 0.1173 0.1448 0.1524
20 0.0701 0.0987 0.1219 0.1283
1 0.1756 0.2473 0.3053 0.3214
5 0.1713 0.2412 0.2978 0.3135
313.15 10 0.1406 0.1981 0.2445 0.2574
15 0.1017 0.1432 0.1768 0.1861
20 0.0774 0.1090 0.1345 0.1416
1 0.1995 0.2810 0.3469 0.3652
5 0.1943 0.2737 0.3379 0.3557
318.15 10 0.1683 0.2371 0.2927 0.3081
15 0.1521 0.2142 0.2645 0.2784
20 0.1171 0.1649 0.2036 0.2143
1 0.1642 0.1741 0.1845 0.1956
5 0.1607 0.1703 0.1805 0.1914
323.15 10 0.1267 0.1343 0.1423 0.1509
15 0.0916 0.0971 0.1029 0.1091
20 0.0771 0.0817 0.0866 0.0918
1 0.1672 0.1772 0.1879 0.1992
5 0.1636 0.1734 0.1839 0.1949
328.15 10 0.1290 0.1368 0.1450 0.1537
15 0.0933 0.0989 0.1048 0.1111
20 0.0785 0.0832 0.0882 0.0935
1 0.1702 0.1804 0.1912 0.2027
5 0.1666 0.1765 0.1871 0.1984
333.15 10 0.1313 0.1392 0.1476 0.1564
15 0.0950 0.1007 0.1067 0.1131
20 0.0799 0.0847 0.0898 0.0952
The high compressibility of the SFC solvent improves the change of density and
therefore the solvent power. With continuous change of temperature and pressure, it is
possible to cover a large spectrum of solvent properties from gas-like to liquid-like values.
As illustrates in Figure 3, for a classical binary solid-fluid mixture, when the pressure
increases, the solubility of a solid solute initially decreases, reaches a minimum, then
exponentially increases up to the critical pressure P* [18]. With further raise of pressure, the
increase of solubility is less important. In the region between the lower crossover pressure P*,
and the upper crossover pressure P**, where the various isotherms converge, an increase of
temperature at constant pressure leads to a decrease in solubility, i.e., a retrograde solubility
behavior.
Figure 3. The nature of the change of the solubility of the model substance along isobars in the
supercritical fluid solvent and the crossing points [19, 20].
The complexity appears in the temperature dependence of the efficiency of the

impregnation caused by the above-mentioned coincidence of the value of pressure
(17.5 MPa), for a data network, presented in Table 1, with the value of the pressure of the
second point of intersection, for the solubility isotherms of the palladium chloride
benzonitrile complex, in supercritical carbon dioxide.
This pressure value (Figure 3), within errors of results of measurements, is an interface
between two opposite trends: decrease in solubility with increasing temperature which leads
to a decrease in the density of the SCF solvent (Р < Р**), and increase in solubility with
increasing temperature, due to an increase in the volatility of the solute (Р > P**).
According to the tabular data, the temperature range 313.15 K to 318.15 K corresponds to
the most favorable range for the impregnation process.
The characteristics of the impregnation process by SC-CO2 in the appropriate ranges of
carbon dioxide flow rate, temperatures and contact times in the impregnation cell, which were
measured in a large range of pressure variation (15.0 - 35.0 MPa), has been presented in
Table 2.
Table 2. Increase in the mass of the catalyst carrier as a result of implementation SC-
CO2-impregnation process, in percent of initial weight
T (K)
Р, (МPа)
308.15 313.15 318.15 323.15 328.15 333.15
15 0.2707 0.2613 0.2503 0.2311 0.1898 0.1503
16 0.2762 0.2768 0.2711 0.2515 0.2017 0.1706
17 0.2675 0.2996 0.3057 0.2714 0.2199 0.1984
18 0.2428 0.3135 0.3338 0.2916 0.2402 0.2357
19 0.2238 0.3002 0.3589 0.3117 0.2747 0.2594
20 0.2009 0.2843 0.3632 0.3509 0.3129 0.2793
21 0.1863 0.2594 0.3517 0.3617 0.3386 0.2911
22 0.1751 0.2336 0.3356 0.3542 0.3401 0.3051
23 0.1649 0.2045 0.3148 0.3107 0.3497 0.3199
24 0.1563 0.1742 0.2909 0.2652 0.3095 0.3244
25 0.1497 0.1627 0.2045 0.2395 0.2714 0.3275
26 0.1403 0.1533 0.1982 0.2206 0.2519 0.3204
27 0.1318 0.1425 0.1919 0.2017 0.2193 0.2913
28 0.1233 0.1321 0.1806 0.1828 0.1967 0.2623
29 0.1149 0.1216 0.1794 0.1739 0.1864 0.2332
30 0.1064 0.1112 0.1731 0.1645 0.1751 0.2041
31 0.0979 0.1007 0.1457 0.1526 0.1646 0.1751
32 0.0894 0.0903 0.1261 0.1351 0.1396 0.1460
33 0.0709 0.0798 0.1054 0.1183 0.1224 0.1369
34 0.0602 0.0694 0.0915 0.1069 0.1120 0.1288
35 0.0564 0.0608 0.0842 0.0905 0.1042 0.1159
Along isobars with pressure values of 15.0 MPa and 16.0 MPa, there is a decrease in
mass with temperature rise, which is distinctly marked, according to the nature of the change
of solubility, corresponding to pressure values lower than the pressure of the second
intersection point. While in the isobars with the pressure values from P = 23 to 35 MPa, there
is an increase in mass with increasing temperature. For the same crossing point, the mass
increases with a rise of temperature.
The results presented in Table 2, confirm previous results of studies carried out on the
solubility of palladium chloride benzonitrile complex in supercritical carbon dioxide [9, 17]
(Figures 4 to 6).
Earlier stated preferences of ranges of implementation of SC-CO2-impregnation process
parameters can be considered in the range of pressures from 19.0 to 21.0 MPa.
The activity of the study samples of catalysts was performed on a experimental micro-
catalytic flow type unit, which has been described in [9, 17].
The test apparatus used for the preliminary treatment of the catalyst (regeneration by
hydrogen), and for further test of the catalyst activity and selectivity, during cleaning fraction
of ethane-ethylene, from acetylene impurity. The work has been carried out according to the
following method which is also described in [9, 17].
Figure 4. Increase in the mass of the catalyst support after implementation of SC-CO2 impregnation
process. Variation of the catalyst mass and solubility of the impregnation material in supercritical
carbon dioxide at a temperature T = 308.15 K.
Figure 5. Increase in the mass of the catalyst support after implementation of SC-CO2-impregnation
Figure 6. Increase in the mass of the catalyst support after implementation of SC-CO2-impregnation
The catalyst sample with a capacity of 0.5 cm3 and particles size of 0.2 to 0.5 mm is
loaded into the central part of the reactor. At the bottom of this reactor a junction of
thermocouple used for the measurement and regulation of the temperature has been located.
Moreover, for additional heating of the incoming gas stream, an inert carrier layer
(floured quartz glass or porcelain with a particle size 0.2 - 0.5 mm) has been poured onto the
catalyst bed.
The restoration of the catalyst was carried out at a temperature close to 473 K, in stream
of hydrogen during two hours.
After that, the temperature in the reactor decreases to the value chosen for the
implementation of the experiment. Then supply of hydrogen stops and the supply of ethane-
ethylene fraction (EEF) of the following composition (volume %): C1-0.22; C2 (ethane)-
13.11; C2 (ethylene)-80.99; C2 (acetylene)-1.05; H2-4.73, with required feed rate of the
volume starts. Composition of EEF has been defined by the customer of the present study.
The initial mixture of ethane-ethylene and the gas mixture after the reactor were analyzed
on a KHROM-4 (“Meta-chrome,” Bauman str. 100, Yoshkar-Ola, Russia) chromatograph
with a flame ionization detector. Components of the mixture have been separated at 343 K,
using a carrier gas (nitrogen) flow rate of 25 cm3/min on a column of 3 m in length, with a 3
mm inner diameter packed with Al2O3 + NaHCO3 (6 wt.%). This material was made in our
University.
The frequency of sampling of the gas mixture at the outlet of the reactor was 1 per hour.
When the complete absence of acetylene has been observed, at certain reactor temperature
and ethane-ethylene mixture flow rate, the volume flow rate was increased to a value at which
the content of acetylene at the outlet of the reactor was 1 to 2 ppm.
Only this ethane ethylene mixture volume rate was used as a characteristic of the activity
of the given catalyst at the selected temperature.
Three samples of palladium catalysts; with the maximum upholding of a complex
(Table 2) in them, were selected for this research:
 The sample (1) is prepared at T = 318.15 K and P = 20 MPa (upholding of 0.3632%).

 The sample (2) is prepared at T = 323.15 K and P = 21 MPa (upholding of a complex
of 0.3617%).
 The sample (3) is prepared at T = 328.15 K and P = 23 MPa (upholding of a complex
of 0.3497%).
The activity of catalysts has been defined according to the method described in the works
[9, 17], and has been estimated relatively to the content of acetylene in the mixture, which is
passed to the hydrogenation reaction of acetylene content in the initial mixture.
The selectivity of the catalyst in the present work has not been established.
The hydrogenation is carried out at a temperature of 373 K. The results of the activity
measurements are shown in Table 3. This table shows that at a temperature T = 373 K, the
activities of the catalyst samples prepared by the method described in this work, impregnation
by supercritical carbon dioxide, are in perfect agreement with the activities of the samples
prepared by a conventional method [9, 17].
The reaction of acetylene, in the ethylene hydrogenation takes place on the catalyst
surface, but not within the volume of pores. Although a measure of the high activity of the
catalysts, prepared under the experimental conditions of the present work, was made at a
temperature of 373 K, this temperature is only in the middle of the range of temperatures,
which are traditionally used in industrial technology and which are between 323 K and 423 K.
Table 3. Activity of palladium catalyst samples
Initial content of acetylene Final content of acetylene Catalyst activity,

Catalyst sample
(peak height, mm) (peak height, mm) %
(1) 205 18 91.21
(2) 214 19 91.12
(3) 209 19 90.09
Table 4. Surface area of prepared palladium catalyst samples
Hinge Width Area of Volume Surface

Height of
Sample plate, Scale of peak peak, of gas, area,
peak (mm)
(g) (mm) (mm2) (cm3) (m2 /g)
Raw Al2O3 0.071 64 134 1.8 15436.8 3.201 220.103
(1) 0.061 64 126 1.2 9676.8 2.02245 161.796
(2) 0.053 64 109 1.2 8371.2 1.74958 161.093
(3) 0.059 64 111 1.3 9235.2 1.93016 159.647
The efficiency of the preparation of the palladium catalyst samples, by supercritical

carbon dioxide impregnation technique, is indirectly confirmed by the measurement of the
surface area of these samples, shown in Table 4.
Frequently, when a high concentration of active metal precipitates on the surface of the
catalyst support, the clogging of the pores of the aluminum oxide occurs, which causes a
significant decrease in the area of the active surface.
When the metal is uniformly distributed throughout the volume of a solid matrix, the
surface area of the catalyst does not decrease significantly.
According to Table 4, it is evident that small decrease in the surface area of the palladium
catalyst samples prepared in this work, in comparison with the pure raw aluminum oxide is
not so important, which indicate a uniform distribution of the impregnation complex in the
volume of the carrier.
3. SYNTHESIS OF PALLADIUM CATALYST BY SUPERCRITICAL СO2

IMPREGNATION METHOD PERFORMED IN DYNAMIC MODE
3.1. Experiments
After the studies of the solubility of palladium chloride complexes in supercritical CO2
were completed and the optimal parameters of the synthesis of the catalyst were determined,
the dynamic impregnation process of Al2O3 was carried out.
Impregnation was performed as described in ref. [20]. The complex to be deposited was
placed into cell (8) (see Figure 7), and the support was set up into the cell located right after
cell (8). The gas flowing through cell (8) dissolved the palladium complex and proceeded into
the cell where the dissolved complex was absorbed by the support.
Figure 7. Diagram of the experimental apparatus for dynamic solubility measurements; (1) - cylinder
filled with CO2; (2) - moisture filter; (3) - refrigerator; (4), (6) - pumps; (5) - high pressure vessel filled
with solvent; (7) - air thermostat; (8) - extractor; (9) - manometer; (10) - pressure controller; (11) -
vessel filled with water.
The impregnation continued for 15 h. Next, we measured the specific surface area of the
catalyst and determined the content of palladium in the sample and its activity.
3.2. Comparison of the Characteristics of a Palladium Catalyst Samples

Synthesized Using the Traditional Method and Dynamic Method
of SC-CO2 Impregnation
The specific surface area of the sample was determined just after impregnation (before
burning and reduction), in order to estimate the depth of penetration of the deposited
component into the porous space of the carrier. It was measured by the nitrogen desorption
method described in ref. [21- 22]. The results are listed in Table 5. The specific surface areas
of the prepared catalysts were smaller to some degree, when compared with the pure carrier
one. The reduction of the surface area means, that some of pores of the carrier were closed by
the metal, however we consider that the impregnation was successful.
Table 5. Surface areas of synthesized catalysts
Peak Peak Gas Specific

Al2O3, impregnated Sample Peak
Scale width, area, volume, surface area,
with weight, g height, mm
mm mm2 cm3 m2/g
Benzonitrile complex 0.056 64 117 1.2 8985.6 1.877 163.620
Cyclohexene complex 0.070 64 132 1.6 13516.8 2.627 183.177
Styrene complex 0.055 64 104 1.3 8652.8 1.808 160.425
From the analysis of the emission spectrum of the samples, the content of palladium in
the samples was:
 the sample impregnated with the benzonitrile complex, 0.022 wt. %;

 the sample impregnated with the styrene complex, 0.15 wt. %;
 the sample impregnated with the cyclohexene complex, 0.04 wt. %.
Preliminary studies were carried out on the palladium content of the catalyst samples. For
comparison, we studied two samples. One was prepared by the traditional impregnation
technique, i.e., an aqueous solution of PdCl2, and the other was a solution of PdCl2 -
benzonitrile complex in benzene. In both cases, after impregnation by SC-CO2, the content of
palladium in the catalyst sample was 0.022 wt. %.
Furthermore, the activity of newly prepared catalysts was measured as it was previously
described. Two different samples were prepared by traditional methods (samples (1) and (2)
were obtained by impregnation from solutions in water and benzene, respectively). Sample
(3) was prepared from a solution of the palladium chloride benzonitrile complex in
supercritical carbon dioxide. Their activities are shown in Table 6.
The reduced value was determined by dividing the measured values of the activity of the
catalyst by a fraction of the metal on the surface of the support. The latter was determined by
microscopy.
Table 6. Catalyst activity of samples (1), (2) and (3)
Hydrogenation
Initial
temperature, K
mixture
333 373
Catalyst sample (1)
Acetylene content (peak height) 204 36 19
Percent of hydrogenation (absolute value) 82.35 90.69
Percent of hydrogenation (reduced value) 82.35 -
Catalyst sample (2)
Acetylene content (peak height) 213.5 110 16
Percent of hydrogenation (reduced value) 61.73
Catalyst sample (3)
Acetylene content (peak height) 218 159 18.5
Percent of hydrogenation (reduced value) 90.15
Table 6, shows that at 333 K, the sample (3) prepared from the benzonitrile complex with
the use of supercritical carbon dioxide has the lowest activity. However, the activity of this
sample at 373 K is the same as the activities of the samples prepared by traditional methods.
This temperature is in the middle of the typical temperature range of industrial processes
(323 to 423 K), allowing us to claim the rather high efficiency of this new approach for the
preparation of catalysts.
Results of surface area evaluation and activity measurements of the catalyst samples
synthesized by supercritical СO2 impregnation of aluminum oxide suggest a large
competitiveness of this approach over traditional methods.
The advantages of this approach should be more evident when a uniform distribution of
the active component throughout the carrier grain volume will be achieved, that is of
fundamental importance. Such uniformity can be reached because of the high degree of
penetration of supercritical fluids in porous structures, as compared to liquid solutions.
CONCLUSION
The results of the present research show the efficiency and attractiveness of SC-CO2
impregnation process, for the production of heterogeneous catalysts, which will be even more
convincing regarding the reactions going on in the volume of pores of a highly porous matrix
of the catalyst support.
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CONCLUSION
This paper describes a new process for the complete recovery of resource that is simple,
effective, economical and environmentally friendly.
Today, there is a higher awareness for a sustainable society, a growing concern about the
effects of greenhouse gas; the fact that the demand for the production of clean petroleum is
rising, implies a business opportunity and an increased market interest for renewable raw
materials and processes, and for the long term survival of companies.
Research on the development of processes for minimization and recycling of spent
catalyst wastes has received increasing attention in recent years because of their hazardous
nature and stringent environmental regulations on their disposal. In this paper, various
methods used for spent catalyst waste reduction at source and the processes available for their
recycling and reuse are reviewed.
Processes of synthesis and regeneration of catalysts used on an industrial scale must be
optimized, to reduce the energy consumption and the harmful impact on the environment. In
the meantime, an audit of traditional and intensive research for new environmentally friendly
and energy-efficient production processes, in various industries, began in the seventies of the
last century. It was suggested that the basis for them, might be the use of sub- and
supercritical fluid media. With regard to the scope of catalyst production and regeneration
processes being discussed, these media are promising as solvents and extractants for
separation, purification, synthesis and impregnation of active components, as well as for
deactivated catalyst regeneration.
The scientific bases of the adsorbent and catalyst regeneration by supercritical fluid
extraction were developed a long time ago. However there is little information, about the
industrial implementation of this process in relation to certain types of catalyst systems.
Nevertheless, it is obvious that due to the wide variety of catalyst systems used in the
industry, it is not possible to establish a universal guide of regeneration technology. This in
turn implies the need of a preliminary study of almost every new process. This paper presents
the results of the study of the process of regeneration of catalysts such as: palladium catalyst
G-58E, nickel on kieselguhr catalysts, active aluminum oxide, LD-265, a mixture of catalysts
Dn-3531 and Criterion 514.The data obtained suggest that the regeneration using supercritical
carbon dioxide modified with various polar additives allows to almost a complete restoring of
the performance of these various types of catalysts. In this case, the regeneration is carried out
at significantly lower temperatures than against the methods of regeneration generally used,
which has a positive effect on the overall performance of catalysts and on the energy
158 Farid Gumerov and Bernard Le Neindre
consumption, associated with the regeneration thereof, which ultimately leads to lower cost of
the ended products.
According to some estimates, the use of supercritical fluid СО2 extraction process in the
catalyst regeneration provides two-fold energy efficiency and a larger number of possible
regeneration cycles. The unique properties of the solvents in the supercritical fluid state also
allow the execution of tasks of application of catalyst active components, that we have
illustrated by the example of synthesis of a palladium catalyst, similar to G-58E catalyst. The
samples obtained using supercritical carbon dioxide are of the same quality as the fresh
catalysts prepared by the manufacturers.
This monograph also describes the results of the study of important thermodynamic
characteristics of the systems involved in the catalyst production and regeneration processes,
which include, first and foremost information on the solubility of the precursors of active
catalyst components and catalyst deactivating compounds in supercritical fluid solvents.
These particular data largely determine the conditions of catalyst regeneration and synthesis
processes that are optimal, from the viewpoints of energy and resource saving.
ACKNOWLEDGMENT
The authors of this study are grateful to the Russian Science Foundation (RSF) for
financial support in the form of a grant (contract No. 14-19-00749).
INDEX
arsenic, ix, 117

A Asia, xi, xv
asymmetry, 16
access, 19, 20, 62
atmosphere, 84
accessibility, 77, 78
atmospheric pressure, 5, 48, 86, 92
acetic acid, xii, 101
atoms, ix
acetone, 8, 9, 23, 30, 36, 37, 45, 69, 102, 110, 128,
attachment, 29
129, 134
audit, 155
acetophenone, 46, 56, 57, 66, 68, 71
automobile, 136
acid, xii, 23, 77, 80, 86, 100, 109, 111, 115, 117, 139
awareness, ix, 155
acidic, viii, xii
activation energy, vii, 71, 140
active centers, 97 B
active site, viii, ix, 77, 78, 109, 117
ADC, 89 base, 4, 50, 77, 80
additives, 34, 37, 102, 128, 132, 155 batteries, 89
adjustment, 17, 85, 120 behaviors, 94
adsorption, ix, 77, 117, 120, 121 bending, 33
adverse effects, 108 benefits, xii, 37
age, 4 benzene, 24, 44, 78, 79, 151
aggregation, xiii bonding, 25
alcohols, 80 bonds, 35, 76, 79
aldehydes, 80 brass, 31
aliphatic amines, 111 bromine, 86, 98, 101, 102, 105
alkane, 114 burn, viii, x, 4, 26
alkenes, 76, 77, 114 burnout, 23
aluminium, 44 butadiene, 4, 24, 76
aluminum oxide, xii, 54, 73, 77, 80, 131, 139, 142, by-products, 77
150, 152, 155
ammonia, 112, 113, 116, 139
aniline, 78 C
annealing, 11
aptitude, 124 cadmium, 31
aqueous solutions, 92 caffeine, 92
aromatic compounds, 76, 78, 113 calcium, ix
aromatic hydrocarbons, 77, 78, 80, 89, 95, 97, 98, calorimetric measurements, 92
99, 113 calorimetry, 118
aromatic rings, 108, 109, 113, 115 capillary, xiii, 5, 29, 30, 46, 54
aromatics, 76, 78, 114 carbon atoms, viii, 76
162 Index
carbon molecule, viii 72, 76, 77, 78, 79, 80, 86, 89, 94, 95, 96, 97, 101,
carbon monoxide, 4 102, 109, 110, 111, 112, 113, 114, 116, 117, 121,
carbon tetrachloride, 90, 91 125, 128, 129, 140, 156
carbonization, 77, 82, 109, 117 compressibility, 57, 58, 61, 145
catalysis, vii, ix, xi, xiii, 2, 23 compression, 88
catalyst deactivation, vii, viii, 4, 33, 109, 116, 117 computation, 17
catalyst replacement, vii, viii, 109 computer, 89
catalytic activity, vii, viii, ix, 67, 78, 100, 101, 102 condensation, 32, 33, 82
catalytic hydrogenation, 3, 24 conditioning, 114
catalytic properties, vii, 39 conductivity, xiii, 30, 120, 121
catalytic system, 2, 141 configuration, 87
cell body, 84 conservation, 39
cellulose, 92 constituents, xi
certificate, 13, 142 construction, xi
challenges, xii, 139 consumption, 79, 112, 114, 115, 156
chemical(s), vii, viii, ix, x, xi, xii, xiii, xiv, 14, 22, contact time, 25, 112, 144, 145
23, 24, 25, 26, 27, 45, 46, 67, 76, 77, 78, 79, 81, contaminant, 6, 8
108, 109, 116, 125, 128, 139, 140 contamination, 22, 109
chemical characteristics, 25, 26, 45, 46, 79 conversion rate, 71, 115, 116
chemical industry, 22, 24, 139 cooling, 4, 28, 48, 50, 83
chemical properties, ix copper, 29, 54, 84, 85
chemical reactions, 116 corrosion, 81, 108, 109, 111, 113
chemical stability, 25 co-solvents, xii, xiv, 8, 35, 36, 37, 45, 68, 69, 70, 77,
chemisorption, ix, 81 83, 90, 94, 95, 101, 110, 120, 124, 127, 130
chlorobenzene, 78 cost, x, xi, xii, 23, 26, 109, 140, 141, 156
chloroform, 23, 29, 32, 36, 37, 45, 47, 69, 70, 71, 90, covering, viii
91, 92, 94, 95, 96, 102, 110, 128, 129, 135 crude oil, 108, 110, 111
chromatograms, 131 crystal structure, 3, 4
chromatography, 33, 45, 56, 120 crystalline, 4
circulation, 28, 83, 84, 85, 112 crystallites, ix
CIS, 19, 153 cycles, x, 3, 4, 13, 22, 23, 27, 28, 117, 118, 156
classes, 8 cyclopentadiene, 79, 80, 89, 100, 102
classification, 78
cleaning, 82, 146
closure, x D
cobalt, xi, 76, 109, 115
data collection, 87
coke, viii, x, xi, xii, 8, 11, 12, 22, 23, 25, 26, 29, 30,
deactivated catalysts, ix, xi, xii, xiv, 1, 2, 97, 107
31, 33, 35, 45, 46, 47, 72, 77, 78, 81, 102, 109,
deactivation, vii, viii, 4, 9, 27, 29, 33, 45, 71, 77, 81,
110, 112, 116, 117, 120, 121, 128, 131
89, 97, 109, 116, 117
coke formation, viii, 25, 26, 33, 45, 109, 112
decomposition, 2, 141
color, 105, 111
degradation, 45, 94
combustion, xiv, 11, 12, 78, 82, 97, 108, 109, 111
dehydration, xii, 43, 44, 45, 55, 56
commercial, viii, xi, xii, xiii, 76, 109, 141
denitrification, 113, 115, 117
compaction, 77, 83, 97
deposition, viii, ix, 2, 3, 22, 25, 45, 78, 81, 97, 117
comparative analysis, 101
deposits, viii, xii, 1, 2, 3, 4, 5, 9, 21, 26, 31, 32, 34,
competition, ix
43, 45, 47, 72, 75, 77, 89, 94, 102, 107, 109, 116,
competitiveness, 152
117, 140
complexity, 26, 145
depth, 11, 112, 114, 115, 151
compliance, ix
derivative thermogravimetry, 46
composition, vii, x, xiii, 3, 4, 7, 25, 29, 33, 44, 46,
derivatives, 60, 108, 111
71, 98, 148
desorption, 120, 121, 131, 132, 151
compounds, viii, xii, xiii, 2, 5, 8, 16, 17, 21, 22, 23,
destruction, 67, 97
24, 26, 27, 33, 34, 35, 37, 45, 48, 67, 68, 69, 71,
deviation, 88
Index 163
dew, 82 evidence, 11, 12

dienes, 77 execution, 156
diesel engines, 111 exothermic effects, 31, 47, 118, 133
diesel fuel, vii, 108, 111, 113 experimental condition, 11, 26, 56, 149
differential scanning calorimetry (DSC), 104, 118, exposure, 117
119, 132, 133, 134, 135 extraction, xii, xiii, xiv, 2, 6, 9, 11, 23, 27, 28, 29,
diffusion, xiii, 23, 33, 144 30, 35, 37, 38, 45, 48, 49, 50, 51, 52, 53, 54, 68,
diffusivities, 4 77, 83, 84, 94, 97, 100, 102, 110, 117, 119, 125,
diffusivity, xiii, 27 127, 128, 129, 130, 139, 156
dimerization, 4, 80 extracts, 29, 83, 95, 96
dimethylsulfoxide, 124, 131
direct measure, 92
dispersion, 29, 76, 109, 115, 140 F
distillation, 111, 114, 117
FAA, 111
distribution, 27, 77, 84, 115, 150, 152
feedstock(s), viii, xi, 76, 77, 78, 108, 109, 111, 112,
divergence, 121
113, 114, 115, 116, 117
diversity, 2
fibers, 76
DMFA, 33
filtration, 140
double bonds, 76, 78, 80, 100
financial support, 157
drying, 25, 30, 82, 140
fixed bed catalytic reactors, vii
DTA curve, 47
flame, viii, 7, 30, 46, 148
dumping, 143
flow value, 123
fluid, xiii, xiv, 2, 3, 4, 5, 6, 11, 13, 14, 23, 27, 28, 29,
E 35, 39, 46, 48, 49, 50, 54, 56, 67, 71, 72, 76, 81,
83, 89, 97, 110, 114, 117, 120, 121, 123, 125,
economic efficiency, x, 23 128, 131, 141, 142, 144, 145, 155, 156
economics, viii, xi fluid extract, xiv, 3, 4, 23, 27, 28, 39, 56, 67, 72, 83,
effluent, 113, 117 89, 97, 142, 155
elastomers, 76 footwear, 76
emission, 113, 151 formation, viii, 2, 4, 22, 26, 33, 37, 46, 47, 71, 72,
endothermic, 31, 44, 47, 118, 120, 133 76, 80, 81, 82, 111, 112, 114, 117, 141
energy, vii, xi, xiii, 2, 3, 4, 11, 13, 16, 23, 28, 39, 77, formula, 62, 86
82, 113, 117, 140, 141, 155, 156 fouling, viii, xi, 81
energy consumption, 28, 117, 141, 155, 156 fragments, 34
energy efficiency, 156 France, xvii, 75
engineering, 4, 24 free energy, 16
enlargement, 2 freedom, xiii
environment, ix, xi, xii, xiv, 2, 27, 155 FTIR, 29, 47, 137
environmental conditions, 114
environmental regulations, ix, x, xii, 22, 155
environmental standards, 108, 110 G
equality, 14
gasoline, vii, 78, 108, 111, 113
equilibrium, xiii, 5, 13, 16, 49, 50, 51, 52, 53, 65, 79,
gel, 5
80, 90, 123, 143
geometry, 115
equipment, xiii, xiv, 22, 108, 120
Germany, 20, 136, 137, 141
ester, 71
glycol, 30, 46
ethanol, 35, 37, 69, 70, 71, 77, 97, 100, 101, 102,
grades, xii, 25
110, 128, 129, 134
granules, 33, 46
ethylene, xii, 1, 3, 4, 7, 11, 22, 30, 31, 39, 76, 140,
graph, 54, 84, 125
146, 148, 149
graphite, 25, 26
Europe, x, xii, xv
greenhouse gas(s), xiv, 155
European Union, 78, 111
groundwater, x, 22
evaporation, 29, 56, 118, 140
164 Index
growth, x, 4, 81 industry(s), vii, viii, x, xi, xii, xiii, 2, 22, 24, 39, 78,
growth rate, x 108, 109, 139, 141, 155
guidelines, x inertia, 27
infrared spectroscopy, 45
initial state, 37
H insulation, 119, 142
integration, 56
halogen, 27
interface, 145
harmful effects, 27, 79
iodine, 100, 101
hazardous materials, ix, x
ionization, 7, 30, 46, 148
hazardous waste, x
IR spectra, 29, 32, 34, 35, 47, 67, 69, 71, 96
health, ix, x
IR spectroscopy, 32, 33, 47, 94
heat capacity, 75, 86, 87, 92, 93, 94
Iraq, 107
heating oil, 111
iron, ix
heating rate, 30, 132
isolation, 76
heavy metals, ix
isomers, 98
heavy oil, vii, 111
isoprene, xii, 21, 22, 24, 25, 26, 32, 33, 35, 76, 89,
height, 10, 25, 31, 84, 131, 132, 149, 151, 152
92
helium, 31, 120
isotherms, 14, 15, 63, 94, 110, 121, 125, 145
heterogeneity, 32, 47, 97
issues, xii, 23
heterogeneous catalysis, vii
Italy, 153
heterogeneous catalysts, xiii, xiv, 152
homogeneous catalysis, vii
homogeneous catalyst, 140 J
hot spots, xi
Hungary, 29, 97 jet fuel, vii, 108, 111
hydrocarbons, vii, 4, 8, 24, 26, 29, 30, 31, 44, 47, 75,
76, 77, 78, 79, 82, 86, 89, 92, 98, 99, 108, 110,
113, 117 K
hydrocracking, 110, 114, 115, 117
KBr, 29
hydrogen, viii, xi, 4, 6, 7, 22, 23, 25, 26, 27, 30, 31,
kerosene, xii, 107, 108, 109, 111, 113, 115, 116, 119
37, 39, 44, 76, 78, 79, 82, 84, 85, 108, 109, 111,
kinetics, vii, 8, 37, 38, 80, 139, 141
112, 113, 114, 115, 116, 117, 146, 148
Korea, 142
hydrogen atoms, 114
hydrogen gas, 76, 78, 116
hydrogen sulfide, xi, 37, 108, 111, 112, 116 L
hydrogenation, xii, 1, 3, 4, 7, 11, 22, 23, 24, 25, 26,
30, 31, 33, 38, 39, 75, 76, 77, 78, 79, 80, 81, 82, landfills, ix, 22
83, 84, 92, 94, 100, 101, 102, 109, 110, 112, 113, laws, x
114, 115, 117, 125, 140, 149, 152 leaching, 23, 81
hydrolysis, 100 legislation, 22
hydroxide, 44 liberation, 117
light, 108, 113, 114, 117
liquid chromatography, 30, 46
I
liquid phase, 25, 49, 50, 79, 84
liquids, 49, 84
identification, 77
localization, 97
impregnation, xiii, xiv, 2, 6, 139, 140, 141, 142, 143,
lubricants, 76
144, 145, 146, 147, 148, 149, 150, 151, 152, 155
improvements, 109
impurities, viii, ix, 3, 22, 24, 29, 44, 65, 108, 111, M
116
industrial changes, vii magnitude, xiii, 17
industrial processes, vii, xi, 2, 22, 152 majority, xii, 23
Index 165
management, xii
manipulation, 6
N
manufacturing, 3
NaCl, 29, 47, 104
market share, x, xii
naphthalene, 8, 79
mass, xiii, 8, 13, 23, 27, 29, 30, 33, 34, 36, 37, 46,
National Bureau of Standards, 104
47, 49, 54, 55, 56, 67, 69, 70, 71, 84, 85, 90, 91,
natural gas, 14, 108
94, 95, 97, 101, 118, 119, 120, 124, 125, 126,
natural resources, xi
127, 128, 129, 130, 133, 134, 135, 143, 144, 146,
nickel, xi, xii, 21, 22, 23, 24, 25, 26, 29, 31, 32, 37,
147, 148
39, 40, 76, 107, 109, 113, 115, 116, 119, 126, 155
mass loss, 47, 97, 119, 120, 133, 134, 135
nitrogen, 7, 10, 27, 77, 82, 85, 94, 108, 109, 110,
materials, xi, 2, 87, 142
111, 112, 113, 115, 116, 117, 120, 121, 131, 132,
matrix, 143, 144, 152
148, 151
matter, xi, 113
nitrogen compounds, 111
measurement(s), xii, xiii, 5, 6, 7, 8, 9, 12, 13, 17, 28,
non-polar, xii, 35, 94, 101, 127
29, 31, 37, 45, 46, 50, 54, 56, 67, 84, 86, 87, 88,
North America, x, xv
89, 92, 93, 94, 97, 100, 101, 110, 121, 123, 139,
145, 148, 149, 150, 152, 154
media, xiii, 2, 3, 5, 23, 27, 39, 45, 46, 72, 125, 155 O
melting, 31, 86, 113
mercury, 48 octane, 78, 108
metal complexes, 2 octane number, 78
metal oxides, 116 oil, vii, x, xii, 4, 22, 23, 29, 76, 107, 108, 110, 111,
metal recovery, xi 113, 114, 117, 139, 140
metallurgy, xi olefins, 4, 22, 76, 80, 115
metals, ix, xi, xii, 2, 17, 22, 26, 76, 78, 108, 110, oligomerization, 4, 76, 77, 79, 80, 82, 89
115, 116, 125, 140 oligomers, 4, 8, 32, 33, 45, 47, 48, 76, 77, 80, 82, 89,
meter, 29, 85 95, 96, 97
methanol, 21, 23, 31, 33, 34, 35, 36, 37, 39, 45, 69, operations, xiv, 82
102, 110, 128, 129, 135 opportunities, xii, xiii, 12
microscopy, 151 optimization, x, xii, xiii, 121
migration, ix, 76, 78 organ, xiv, 2, 19, 81, 117
mixing, 16, 29, 61, 62, 75, 88, 92, 93 organic compounds, 24, 41
models, 92 organic solvents, xi, xiii, 23, 27
modifications, xiii ownership, x
moisture, 5, 6, 30, 118, 150 oxidation, viii, 11, 26, 32, 37, 44, 47, 77, 82, 97, 102,
moisture content, 30 109, 117
molar volume, 14, 56, 57 oxidation products, 32
mole, 14, 15, 16, 56, 57, 58, 88, 121, 124 oxidation rate, 44
molecular oxygen, 71 oxygen, viii, xi, 4, 23, 26, 44, 77, 82, 108, 109, 110,
molecular weight, viii, 4, 108, 113 111, 112, 117
molecules, viii, ix, xii, 4, 15, 35, 76, 109, 114, 140
molybdenum, xi, xii, 76, 107, 109, 115, 116, 119,
126 P
MOM, 8, 29
monomers, xiv Pacific, xi, xv
morphology, 76 paints, 78
Moscow, 20, 39, 40, 41, 72, 73, 103, 105, 136, 137, palladium, xii, xiv, 1, 2, 3, 5, 6, 13, 14, 15, 17, 18,
152, 153 19, 75, 76, 77, 78, 79, 81, 82, 83, 85, 89, 95, 102,
motivation, vii 139, 140, 141, 142, 143, 144, 145, 146, 149, 150,
MPC, 44, 45, 48, 55, 56, 67, 71, 72 151, 154, 155, 156
MTI, 7 pathway, vii
multi-component systems, xiii petrochemical industry, vii
petrochemicals, vii, x
166 Index
petroleum, vii, x, 76, 78, 102, 105, 108, 109, 112,

113, 136, 155
R
petroleum distillates, 105
race, 116
pharmaceuticals, 78
radicals, viii
phenol, 46
raw materials, ix, xiii, 22, 79, 82, 97, 155
phenolphthalein, 100
reactant(s), vii, 25, 44, 71, 76, 77, 78
phosphorus, ix
reaction medium, xiv
physical properties, x, 17, 81
reaction rate, 38, 71, 112, 140
physicochemical properties, 114
reaction temperature, 37
pipeline, 84
reaction time, 71
piperylene, 24, 89, 98
reactions, viii, 2, 3, 4, 22, 24, 25, 77, 78, 79, 80, 81,
plants, xii, 3, 4, 23, 44
82, 97, 109, 110, 112, 113, 114, 115, 117, 140,
plastics, vii, 76, 114
152
platform, 6
reactivity, 76, 79, 80
platinum, 29, 46, 76, 84, 132
reagents, xii, 115
PLP, 1
recall, 26
poison, ix, 22
recovery, ix, xi, xii, 22, 23, 27, 31, 37, 38, 39, 101,
polar, xii, 11, 21, 34, 35, 36, 37, 43, 45, 67, 68, 71,
155
72, 75, 77, 94, 101, 102, 107, 125, 127, 128, 129,
recrystallization, 117
132, 155
recycling, xi, 23, 79, 155
polarity, 37, 77, 90, 102, 129
refinery capacity, xi
pollutant(s), 45, 46, 50, 66, 110, 120, 124, 132
refractive index, 29
pollution, xi
regenerate, ix, xi, xii, xiv, 23, 28, 33, 50, 56, 66, 89,
polyisoprene, 75, 76, 89, 90, 92, 93, 94
109, 115
polymer(s), x, xiv, 3, 4, 22, 45, 46, 47, 48, 64, 76,
regulations, x, 78, 109
78, 82, 92, 114
regulatory changes, x
polymerization, viii, 3, 64, 76, 77, 78, 80
relaxation, 62
polymerization process, 3
requirement(s), x, xiii, 22, 101, 108, 109, 110, 111,
polystyrene, 48, 71
141
porosity, 2, 25, 39, 77, 82, 114
research institutions, xiv
porous materials, 27
researchers, 23, 28, 83, 144
porous space, 151
reserves, 111
potassium, 101
residue(s), vii, xii, xiii, 4, 22, 71, 72, 82, 94, 96
power plants, 108, 110
resins, 45, 47, 76, 82
precipitation, 140
resistance, 84
preparation, 2, 3, 5, 22, 23, 44, 80, 140, 149, 152
resources, xiv, 140
pressure gauge, 5, 7, 28, 48, 87, 119, 120, 121
restoration, 37, 77, 148
probability, 2, 4, 16
restrictions, 115
production technology, xiv
rhenium, 76
propylene, 44, 76
rings, 109
protection, 115
risk(s), ix, x, xiv, 46, 109
public health, 111
room temperature, 29, 92, 93, 101
pumps, 6, 84, 108, 113, 150
rubber, 76
purification, 2, 77, 140, 155
rules, 16, 61, 62, 109
purity, xi, 13, 86, 142
Russia, xii, xvii, 1, 21, 27, 41, 43, 44, 73, 74, 75,
pyrolysis, 22, 76, 78, 140
107, 108, 111, 137, 139, 140, 148
Q
S
quality control, xii
safety, xii, 26, 27, 109, 111
quality standards, 111
salts, 140
quantification, 16
saturated hydrocarbons, 29
quartz, 7, 56, 84, 148
Index 167
saturation, 17, 54, 84, 109, 112, 114, 115, 125, 143 substitutions, 78
savings, xi, 2, 4 substrate, 109, 115
scope, 84, 141, 155 sulfate, 27
selectivity, vii, viii, 4, 22, 25, 35, 56, 71, 72, 76, 77, sulfur, ix, 26, 27, 37, 108, 109, 110, 111, 112, 113,
78, 127, 140, 146, 149 114, 115, 116, 117, 118
sensitivity, 8, 16, 29, 88 sulfur dioxide, 108, 110, 117
sensor(s), 84, 119, 120 sulfuric acid, 111, 139
shade, 46 supercritical fluid, xiii, xiv, 2, 3, 4, 5, 6, 11, 14, 20,
shape, 77, 97 23, 27, 28, 39, 46, 49, 56, 67, 71, 72, 83, 89, 97,
side chain, 80 110, 117, 121, 124, 125, 128, 131, 141, 142, 144,
signals, 84 145, 152, 155, 156
silica, 5, 31, 115 supplier, 142
simulation, xiii surface area, viii, ix, xiv, 3, 8, 10, 25, 44, 45, 76, 79,
sintering, viii, ix, xi, xiv, 2, 4, 37, 39, 46, 77, 82, 83, 81, 110, 120, 131, 149, 150, 151, 152, 154
117 surface layer, 140
SiO2, 26, 78, 116 surface structure, 117
smoothing, 84 surface tension, xiii
society, xiii, 155 survival, 155
sodium, 100, 101 synthesis, xiii, xiv, 2, 3, 13, 24, 100, 140, 141, 142,
sodium hydroxide, 100 150, 155, 156
software, 30, 46
sol-gel, 140
solid matrix, 143, 150 T
solid waste, 22
tanks, 111
solubility, xii, xiii, xiv, 1, 2, 3, 5, 6, 8, 11, 13, 14, 15,
target, 3, 44, 115
17, 23, 28, 43, 45, 48, 49, 50, 56, 57, 62, 63, 64,
techniques, xiii, xiv, 1, 13, 21, 43, 75, 82, 107, 131,
65, 66, 89, 90, 91, 92, 94, 101, 104, 107, 110,
140
120, 121, 122, 123, 124, 127, 141, 143, 145, 146,
technologies, x, xii, xiii, 2, 22, 27, 127, 140
147, 148, 150, 156
technology, vii, ix, x, xii, xiii, xiv, 2, 5, 11, 23, 40,
solution, 5, 9, 14, 29, 39, 48, 49, 50, 62, 93, 100,
44, 149, 155
101, 140, 143, 144, 151
temperature dependence, 145
solvent molecules, 127
testing, 31, 37, 84
solvents, xii, xiii, xiv, 3, 5, 8, 35, 36, 37, 45, 68, 69,
the palladium catalyst, xiv, 1, 81, 149, 150
70, 77, 78, 83, 90, 94, 95, 101, 110, 120, 124,
thermal analysis, 8, 11, 23, 29, 31, 46, 97, 107, 132
127, 130, 137, 141, 155, 156
thermal energy, 79
soot production, xiv
thermal stability, 4
species, viii, 45, 77, 78, 81
thermal treatment, 23, 77, 82
specific surface, 1, 8, 9, 25, 77, 82, 107, 115, 131,
thermodynamic equilibrium, 80
151
thermograms, 88
specifications, 108, 111
thermogravimetric analysis, 132
stability, vii, 76, 81, 111, 141
thermogravimetry (TGA), 8, 31, 45, 46, 47, 97
standard deviation, 124
threats, x
state(s), viii, xii, xiii, 1, 2, 13, 14, 16, 23, 27, 35, 43,
tin, 31
57, 65, 66, 80, 89, 92, 107, 110, 124, 140, 156
toluene, 78, 79, 100
steel, 29, 30, 84
toxic gases, 22
stock, 98, 100
toxicity, 77
storage, 111
transformation, 81
stretching, 33
transport, xi, 25, 76
structural changes, ix, 94
treatment, xii, 2, 4, 26, 37, 39, 80, 89, 96, 109, 117,
structure, viii, ix, 2, 4, 34, 67, 97, 109, 114
146
styrene, 1, 2, 13, 15, 18, 43, 44, 45, 46, 47, 48, 49,
tungsten, 76, 115
50, 51, 52, 53, 56, 57, 63, 64, 65, 66, 67, 71, 72,
79, 80, 81, 89, 95, 97, 101, 102, 151
168 Index
U W
uniform, 31, 84, 150, 152 Washington, 153

universal gas constant, 14 waste, x, xii, xiii, 22, 23, 140, 155
USA, x water, xiv, 6, 11, 22, 31, 44, 45, 47, 55, 56, 104, 111,
112, 117, 150, 151
water vapor, 45
V wave number, 33
weight changes, 8, 12
vacuum, 108, 114, 117
weight loss, 11, 30, 32
valence, 81
windows, 29
valve, 6, 7, 28, 30, 31, 54, 83, 89, 119, 120
Wisconsin, 40
vapor, xiii, 14, 17, 44, 55, 56, 96, 112, 123, 124, 127
working conditions, 139
variables, 112
worldwide, 111
variations, 10, 84, 94
varieties, 25
vehicles, 108, 110, 111 Y
velocity, 25, 84, 112, 115
vessels, 84 yield, viii, 68, 71, 77, 80, 83, 94, 108, 109, 114, 117
viscosity, xiii, 5, 23, 27, 29
volatility, 56, 57, 61, 64, 145
Z
zinc, ix, 31

2016 (Book) Regeneration of Spent Catalyst and Impregnation of Catalyst by S

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2016 (Book) Regeneration of Spent Catalyst and Impregnation of Catalyst by S

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CHEMISTRY RESEARCH AND APPLICATIONS

REGENERATION OF SPENT CATALYST

Additional books in this series can be found on Nova’s website

Additional e-books in this series can be found on Nova’s website

REGENERATION OF SPENT CATALYST

NOTICE TO THE READER

Library of Congress Cataloging-in-Publication Data

ISBN:  H%RRN

Published by Nova Science Publishers, Inc. † New York

Chapter 6 Synthesis of the Palladium Catalyst by Supercritical

Deactivation by poisoning involves chemisorption on the active sites of the competing

Safe disposal of a spent catalyst is a major environmental problem, as landfill disposal is

Farid M. Gumerov – Professor, Federal State Budgetary Educational Institution of

REGENERATION OF PALLADIUM CATALYSTS

T. R. Bilalov1, F. M. Gumerov1,*, F. R. Gabitov1,

Keywords: catalyst regeneration, catalyst activity, supercritical carbon dioxide, solubility,

 the preparation of high-porosity materials which are potential catalyst carriers;

2. HYDROGENATION PROCESS OF ETHANE-ETHYLENE FRACTION;

1. Target hydrogenation reaction of acetylene to ethylene

C2H2 + H2 → C2H4 H298K = - 172 MJ/kmol.

2. Undesirable effect of hydrogenation of ethylene to ethane

C2H4 + H2 → C2H6 H298K = - 137 MJ/kmol.

3. MATERIALS, EQUIPMENTS, APPLIED RESEARCH METHODS

4. SOLUBILITY COMPOUNDS OF DEACTIVATION OF CATALYST

5. REGENERATION OF PALLADIUM CATALYSTS G-58E

Table 1. Surface areas of G-58E catalyst samples

Peak Peak Peak Volume of Specific

6. COMPARISON OF CHARACTERISTICS OF REGENERATED

Table 2. Activities of G-58E catalyst samples

Rate of hydrogenation of acetylene (%) as a function of

7. SOLUBILITY OF PALLADIUM CHLORIDE

Table 3. Variation of the solubility of palladium chloride benzonitrile complex in

T = 308.15 K T = 318.15 K T = 328.15 K

Table 4. Variation of the solubility of palladium chloride styrene complex in

T = 308.15 K T = 318.15 K T = 328.15 K

Table 5. Variation of the solubility of palladium chloride cyclohexene complex in

T = 308.15 K T = 318.15 K T = 328.15 K

The other quantities in Equation (3) are:

bij  (bii b jj )1/ 2

ai  0.45724 R 2Tc2 i T  / Pc , (7)

bi  0.0778 RTc / Pc , (8)

  1.000  log10 Psat / Pc Tr 0.7 (10)

Table 6. Solute and solvent critical parameters

Critical parameters Palladium CO2 [18]

Table 7. Binary interaction coefficients

Supercritical carbon dioxide-organometallic Temperature, Binary interaction coefficient,

[13] Nelsen, F. M., Eggertesen, F. T. Determination of the Surface Area. Adsorption

REGENERATION OF NICKEL ON KIESELGUHR

R. F. Gallyamov1, А. А. Sagdeev1, F. M. Gumerov2,*

Keywords: acetylene, isoprene, catalyst regeneration, catalyst activity, nickel on kiеselguhr

2. PROCESS OF THE SEPARATION OF ACETYLENE COMPOUNDS FROM

Under these conditions, there is also a secondary reaction of hydrogenation of isoprene to

Table 1. Composition of kieselguhr

Table 2. Physical and chemical characteristics of fresh catalyst

Mass fraction of nickel, less than 54 wt.%

a) The possibility of local overheating of the catalyst, as well as incomplete removal of

3. MATERIALS, EQUIPMENT, APPLIED RESEARCH METHODS

The processes of catalyst and adsorbent regeneration by supercritical fluids are

4. REGENERATION OF NICKEL ON KIESELGUHR CATALYST USED

Figure 4. IR spectrum of nickel on kieselguhr catalyst deposits.

Table 3. Data from the joint analysis of deactivated catalyst by

Temperature, K Name Extract, wt.%

Extract Content Extract, wt. %

ISBN: H%RRN