Title of Invention

PROCESS FOR PRODUCING A HYDROCARBON COMPONENT

Abstract The invention relates to a process for producing a new type of high-quality hydrocarbon base oil of biological origin. The process of the invention comprises ketonisation, hydrodeoxygenation, and isomerization steps. Fatty acids and/or fatty acid esters based on a biological raw material are preferably used as the feedstock.
Full Text

Technical field
The invention relates to a process for producing a hydrocarbon component, and
particularly a process for producing a high-quality branched saturated
hydrocarbon component of biological origin to be used as a new kind of base oil.
The process comprising ketonisation, hydrodeoxygenation, and isomerization
steps utilizes as feedstock raw material of biological origin eventually derived
from plant oils, animal fats, natural waxes, and carbohydrates. Also corresponding
synthetic materials and combinations thereof may be used as feedstock.
State of the art
Base oils are commonly used for the production of lubricants, such as lubricating
oils for automotives, industrial lubricants and lubricating greases. They are also
used as process oils, white oils and metal working oils. Finished lubricants consist
of two general components, lubricating base oil and additives. Lubricating base
oil is the major constituent in these finished lubricants and contributes
significantly to the properties of the finished lubricant. In general, a few
lubricating base oils are used to manufacture a wide variety of finished lubricants
by varying the mixtures of individual lubricating base oils and individual
additives.
Base oils according to the classification of the American Petroleum Institute (API)
Group in or IV are used in high-quality lubricants. API base oil classification is
shown in Table 1.
Table 1. API base oil classification


Oils of the Group III are base oils with very high viscosity indices (VHVI)
produced by modern methods from crude oil by hydrocracking, followed by
isomerization of the waxy linear paraffins to give branched paraffins. Oils of
Group III also include base oils produced from Slack Wax paraffins from mineral
oils, and from waxes obtained by Fischer-Tropsch synthesis (GTL waxes) for
instance from coal or natural gas using corresponding isomerization techniques.
Oils of Group IV are synthetic polyalpha-olefins (PAO). A similar classification is
also used by ATTEL (Association Technique de l'Industrie Europeenne des
Lubrifiants, or Technical Association of the European Lubricants Industry), said
classification also comprising Group VI: Polyinternalolefins (PIO). In addition to
the official classification, also Group II+ is commonly used in this field, this
group comprising saturated and non-sulfurous base oils having viscosity indices
of more than 110, but below 120. In these classifications saturated hydrocarbons
include paraffinic and naphthenic compounds, but not aromatics.
There is also available a definition for base stocks according to API 1509 as: "A
base stock is a lubricant component that is produced by a single manufacturer to
the same specifications (independent of feed source or manufacturer's location);
that meets the same manufacturer's specification; and that is identified by a unique
formula, product identification number, or both. Base stocks may be
manufactured using a variety of different processes." Base oil is the base stock or
blend of base stocks used in API-licensed oil. The known base stock types are 1)

Mineral oil (paraffmic, naphthenic, aromatic), 2) Synthetic (polyalphaolefms,
alkylated aromatics, diesters, polyol esters, polyalkylene glycols, phosphate
esters, silicones), and 3) Plant oil.
Already for a long time, especially the automotive industry has required lubricants
and thus base oils with improved technical properties. Increasingly, the
specifications for finished lubricants require products with excellent low
temperature properties, high oxidation stability and low volatility. Generally
lubricating base oils are base oils having kinematic viscosity of about 3 cSt or
greater at 100 °C (KV100); a pour point (PP) of about -12 °C or less; and a
viscosity index (VI) about 120 or greater. In addition to low pour points also the
low-temperature fluidity of multi-grade engine oils is needed to guarantee that in
cold weather the engine starts easily. The low-temperature fluidity is
demonstrated as apparent viscosity in cold cranking simulator (CCS) tests at -5 to
-40 °C temperature. Lubricating base oils having KV100 of about 4 cSt should
typically have CCS viscosity at -30 °C (CCS-30) lower than 1800 cP and oils
having KV100 of about 5 cSt should have CCS-30 lower than 2700 cP. The lower
the value is the better. In general, lubricating base oils should have Noack
volatility no greater than current conventional Group I or Group II light neutral
oils. Currently, only a small fraction of the base oils manufactured today can be
used in formulations to meet the latest, most demanding lubricant specifications.
It is no longer possible to produce lubricants complying with the specifications of
the most demanding car manufacturers, from conventional mineral oils. Typically,
mineral oils often contain too high concentrations of aromatic, sulfur, and
nitrogen compounds, and further, they also have a high volatility and a modest
viscosity index, that is, viscosity-temperature dependence. Moreover, response of
mineral oils to antioxidant additives is often low. Synthetic and so-called semi-
synthetic base oils play an increasingly important role especially in automotive
lubricants, such as in engine and gear oils. A similar development can be seen for
industrial lubricants. Service life of lubricants is desirably as long as possible, thus

avoiding frequent oil changes by the user, and further allowing extended
maintenance intervals of vehicles for instance in commercial transportation. In the
past decade, engine oil change intervals for passenger cars have increased five
fold, being at best 50,000 km. For heavy-duty vehicles, engine oil change
intervals are at present already on the level of 100,000 km.
The production of lubricants is influenced by increasingly common "Life Cycle
Approach" (LCA) concerning environment, health and safety factors of the
product. What is aimed with LCA are an extended service life of the product, and
minimal drawbacks to the environments associated with the production, use,
handling and disposal of the product. Longer oil change intervals of high-quality
base oils result in decreased consumption of non-renewable mineral crude oil
based raw materials, and lower amounts of hazardous waste oil products.
In addition to the demands for engine technology and base oil production, also
strict environmental requirements direct the industry to develop more
sophisticated base oils. Sulfur free fuels and base oils are required in order to gain
full effect of new and efficient anti-pollution technologies in modern vehicles and
to cut emissions of nitrogen oxides, volatile hydrocarbons and particles, as well as
to achieve direct reduction of sulfur dioxide in exhaust gases. The European
Union has decided that these fuels shall be available to the market from 2005 and
they must be the only form on sale from 2009. Conventional mineral oil base oils
contain sulfur, nitrogen, aromatic compounds, and typically also volatile
compounds. They are less suitable for new engines and thus also environmentally
more detrimental than newer sulfur and aromatic free base oils.
Nowadays, the use of recycled oils and renewable raw materials in the production
of lubricants is frequently an object of interest. The use of renewable raw
materials of biological origin instead of non-renewable fossil raw materials to
produce hydrocarbon components is desirable, because the fossil raw materials
are exhaustible and their effect on environment is detrimental. Problems

associated with recycled oils include complicated purification and reprocessing
steps to obtain base oils with high quality. Further, the development of a
functioning and extensive recycling logistic system is expensive.
For the time being, only esters are used in lubricants of renewable and biological
origin. The use of said esters is limited to a few special applications such as oils
for refrigeration compressor lubricants, bio-hydraulic oils and metal working oils.
In normal automotive and industrial lubricants, they are used mainly in additive
scale. High price also limits the use of esters. In addition, the esters used in engine
oil formulations are not interchangeable with other esters without performing new
engine tests, even in cases where the chemical composition of the substituting
ester is in principle similar. Instead, base oils consisting of pure hydrocarbon
structure are partly interchangeable with each other. There are also some technical
problems associated with esters. As polar compounds, esters suffer greater seal-
swelling tendency than pure hydrocarbons. This has created lot of problems
relating to elastomer in hydraulic applications. In addition, ester base oils are
hydrolyzed more easily producing acids, which in turn cause corrosion on
lubricating systems. Further, even greater disadvantage of esters is that additives
developed for non-polar hydrocarbon base oils are not effective for ester base oils.
Ketones are commonly used as antifoam agents, mould release agents, and in
mixtures with paraffin as metal coatings, as well as components of printing inks.
Processes for producing ketones are known in the art, where the functional groups
of the feed molecules react with each other forming a ketone. The carbon number
of the ketone formed is reduced by one compared to the sum of the carbon
numbers of the reacted feed molecules. Metals or oxides of alkaline earth metals
are used as catalysts. EP 591297 describes a method for producing a ketone from
fatty acids by pyrolysis reaction using a magnesium oxide catalyst. EP 0457665
discloses a method for producing ketones from triglycerides, fatty acids, fatty acid
esters, fatty acid salts, and fatty acid anhydrides using a bauxite catalyst
containing iron oxide.

Ketones may be reduced to paraffins using Wolff-Kishner reduction. The reaction
involves converting a ketone to the corresponding hydrazone (H2NNH2) and
decomposition of this intermediate in the presence of base at about 200 °C to yield
the reduced alkyl derivative and nitrogen. Ketone is normally heated with
hydrazine hydrate and sodium hydroxide at 100 - 200 °C temperature. Diethylene
glycol or dimethyl sulfoxide is used as solvent Alternatively, direct reduction of
the carbonyl group to give a methylene group may be carried out with
Clemmensen reduction reaction catalyzed by amalgam zinc and hydrochloric acid.
Also a method for reducing ketones by catalytic hydrogenation with palladium on
carbon catalyst at 50 - 150 °C temperature, under a hydrogen pressure between
0.1 and 0.5 MPa is known. With non-noble metals such as nickel, a higher
temperature of nearly 200 °C, and a hydrogen pressure of 30 MPa must be used as
disclosed in Ullmanns Encyclopadie der technischen Chemie, 4. neubearbeitete
und erweiterte Auflage, Band 13, Verlag Chemie GmbH, Weinheim 1983,
Hydrierung p. 140.
FI 100248 presents a process with two steps wherein middle distillate is produced
from plant oil by hydrogenation of the carboxylic acids or triglycerides of said
plant oil to yield linear normal paraffins, followed by isomerization of said n-
paraffins to give branched paraffins. The hydrogenation was performed at a
temperature ranging from 330 to 450 °C, under a pressure of higher than 3 MPa
and liquid hourly space velocity (LHSV) being from 0.5 to 5 1/h. The
isomerization step was carried out at 200 to 500 °C temperature, under elevated
pressure, and LHSV being from 0.1 to 10 1/h.
EP 774451 discloses a process for isomerization of tatty acids or fatty acid alkyl
esters. The isomerization of unsaturated fatty acids or fatty acid alkyl esters is
performed using clay or another cationic catalyst. In addition to the main product,
also feedstock dimers are obtained. After distillation, unsaturated branched fatty
acids or fatty acid alkyl esters are obtained as the product.

GB 1 524 781 discloses a process for producing hydrocarbons from plant oil. In
this process, the plant oil feed is pyrolyzed in three zones in the presence of a
catalyst at temperature of 300 - 700 °C. In the process hydrocarbons of the gas,
gasoline, and diesel classes are obtained. They are separated and purified.
Starting materials originating from biological sources contain high amounts of
oxygen. In processing oxygen is converted to water, carbon monoxide, and carbon
dioxide. In addition, starting materials of biological origin often contain nitrogen,
sulfur and phosphorus known as catalyst poisons and inhibitors of noble metal
catalysts. They cause decreased service life of the catalyst, and make frequent
regeneration of the catalysts necessary. Noble metal catalysts are used in
isomerization processes. They are very expensive and highly sensitive to catalyst
poisons.
Typical basic structural unit of plant and fish oils and animal fats is a triglyceride.
Triglyceride is an ester of glycerol with three fatty acid molecules having the
structure below:

wherein R1, R2 and R3 represent C4-C26 hydrocarbon chains. The length of the
hydrocarbon chain is mainly 18 carbons (C18). C18 fatty acids are typically
bonded to the middle hydroxyl group of glycerol. Typical carbon numbers of the
fatty acids linked to the two other hydroxyl groups are even, being generally
between carbon numbers C14 and C22.
Prior to processing, starting materials of biological origin are commonly
pretreated with suitable known methods such as thermally, mechanically for

instance by means of shear force, chemically for instance with acids or bases, or
physically with radiation, distillation, cooling, or filtering. The purpose of
chemical and physical pretreatments is to remove impurities interfering with the
process or poisoning the catalysts, and reduce unwanted side reactions.
The pretreated biological raw material is often also preprocessed using a known
method such as hydrolysis, transesterification, reduction, or saponification. Fatty
acids may be produced from triglycerides by thermal pyrolysis treatment. In a
hydrolysis reaction, oils and fats react with water yielding free fatty acids and
glycerol as the product. Three main processes for the industrial production of fatty
acids are known: Vapor splitting of triglycerides under high pressure, basic
hydrolysis, and enzymatic hydrolysis. In the vapor splitting process, the
hydrolysis of triglycerides using steam is carried out at temperatures between 100
and 300 °C, under a pressure of 1 - 10 MPa, preferable conditions being from 250
to 260 °C and from 4 to 5.5 MPa. Metal oxides like zinc oxide may be added as
the catalyst to accelerate the reaction. High temperature and pressure contribute to
the dissolution of fats in water.
Fatty acid esters like triglycerides may be transesterified with an alcohol to obtain
fatty acid alkyl esters. In the transesterification reaction the triglyceride structure
is decomposed, the carboxylic acid yielding an ester with the alcohol, whereas the
glycerol moiety of the triglyceride is liberated. Typically, methanol is used as the
alcohol, but also other C1-C11 alcohols may be used. Sodium and potassium
hydroxides dissolved in excess in methanol are used as catalysts. Typical
conditions for the transesterification are as follows: Temperature between 60 and
70 °C, pressure between 0.1 and 2 MPa. Esterification of free carboxylic acids
with alcohol requires higher temperature and pressure (e.g. 240 °C and 9 MPa), or
acidic conditions. For this reason, any free fatty acids present in the
transesterification feed should be removed. Alternatively they can be separately
esterified for instance using a sulfuric acid catalyst either before or after
transesterification.

Acidic groups of fatty acids may be directly reduced to alcohols with lithium
aluminium hydride, the double bonds thus remaining in alcohols, or in a manner
used in industrial scale by hydrogenation of the fatty acid alkyl esters produced by
transesterification to saturated alcohols. In the hydrogenation reaction, the alcohol
moiety used for the transesterification is liberated and may be recycled. Fatty acid
alkyl esters are reduced with metal catalysts, typically with copper chromite under
a hydrogen pressure between 25 and 30 MPa, at 210 °C. The C1-C3 alcohol
liberated in the reaction is separated from the heavier fatty alcohol. Also
chromium, iron or preferably rhodium activated nickel catalysts may be used at a
temperature between 200 and 230 °C and under a hydrogen pressure of 25 MPa.
Unsaturated alcohols are obtained in case a copper-zinc catalyst is used.
Fatty aldehydes may be produced from fatty alcohols by removing hydrogen in a
dehydrogenation reaction. The reaction is opposite to the hydrogenation reaction
of alcohols, and thus endothermic. In the dehydrogenation reaction corresponding
hydrogenation catalysts are used but the temperature is higher, and thus side
reactions such as cracking, isomerization, cyclization, and polymerization are
possible. Supported copper chromite catalysts are typically used for producing
aldehydes from alcohols. In gas phase dehydrogenation, typically a temperature
between 250 and 400 °C, and a pressure between 0.1 and 0.5 MPa are used.
Moreover, it is generally known that corresponding aldehydes can be produced
from alcohols using alumina, silica-alumina, hafnium oxide and zirconium oxide
as catalyst. The products of the process are controlled by changes in process
temperature. At low temperatures ethers are obtained, high temperatures give
aldehydes, whereas olefins are typically obtained at 300 - 350 °C.
Oils, fats and free fatty acids may be saponified in aqueous solutions by reaction
with metal hydroxides such as alkali metal hydroxides yielding metal salts of fatty
acids, and glycerol. In addition to sodium hydroxide, also for instance potassium
oxide or zinc oxide may be used. In this case the formed soap has poor solubility

in water and is readily isolated from the glycerol, which is soluble in water. In a
traditional saponification process, the basic hydrolysis of triglycerides is
performed at about 100 °C, under normal pressure.
Neither the use of heteroatom containing starting materials of biological origin in
a process for producing high-quality saturated base oils has not been disclosed,
nor there are any reports about the use of heteroatom containing, optionally
thermally and/or chemically and/or physically and/or mechanically treated
intermediate materials of biological origin in a process for producing high-quality
saturated base oils.
On the basis of the above teaching it may be seen that there is an obvious need for
an alternative process for producing branched saturated hydrocarbon components
from starting materials of biological origin. There is also a need for nonpolar
saturated base oils complying with the quality requirements for high-quality base
oils, said base oils being preferably of biological origin and having more
preferable effects on the environment and for end users than traditional mineral
base oils.
Object of the invention
An object of the invention is a process for producing a hydrocarbon component.
A further object of the invention is a process for producing a hydrocarbon
component using starting materials of biological origin.
Another object of the invention is a process for producing a new type of base oil.
Still another object of the invention is a process for producing a diesel component.
Further, another object of the invention is a process for producing a gasoline
component.

Another object of the invention is a process for producing saturated base oil and
diesel component from starting materials of biological origin, said products
mainly not containing heteroatoms.
An object of the invention is moreover a base oil complying with the requirements
of the API Group III.
The characteristic features of the process and base oils of the invention are
presented in the appended claims.
General description of the invention
The process of the invention for producing a hydrocarbon component, and
particularly a high-quality saturated hydrocarbon base oil of biological origin,
comprises a ketonisation step, a hydrodeoxygenation step and an isomerization
step. The isomerization step refers here both to isomerization of unsaturated
carboxylic acids and alkyl esters of carboxylic acids, particularly unsaturated fatty
acids and fatty acid alkyl esters, and also isomerization of paraffins. Isomerization
of fatty acids and fatty acid alkyl esters is performed prior to the ketonisation step,
whereas the isomerization of paraffins is carried out following the ketonisation
and HDO steps.
Carboxylic acids and their derivatives or combinations thereof, preferably fatty
acids, fatty acid esters, fatty alcohols, fatty aldehydes, anhydrides of fatty acids, or
metal salts of fatty acids of biological origin, are used as the feedstock of the
process. Said starting materials of biological origin may be pretreated if
necessary, and/or preprocessed using known methods.
Here, saturated base oil comprises saturated hydrocarbons. The term "saturated
hydrocarbons" refers to paraffinic and naphthenic compounds, but not to

aromatics. Paraffinic compounds may either be branched or linear. Naphthenic
compounds are cyclic saturated hydrocarbons, or cycloparaffins, typically derived
from cyclopentane or cyclohexane. A naphthenic compound may comprise a
single ring structure (mononaphthene) or two isolated ring structures (isolated
dinaphthene), or two fused ring structures (fused dinaphthene) or three or more
fused ring structures (polycyclic naphthenes or polynaphthenes).
Here, ketonisation refers to the ketonisation reaction of carboxylic acids and the
derivatives thereof, particularly fatty acids, corresponding esters, alcohols,
aldehydes, anhydrides, and metal salts. In the reaction the functional groups of the
feedstock react with each other yielding ketones. The ketonisation reaction of two
carboxylic acids proceeds through an anhydride intermediate to give a ketone,
water and carbon dioxide liberating in the reaction. In the pyrolytic ketonisation
reaction of anhydrides and metal salts carbon dioxide is liberated. For alcohols
and esters, the ketonisation reaction proceeds via aldehydes to give a Tishchenko
ester and further to ketones, for aldehydes via Tishchenko esters to ketones. In
these two last reactions carbon monoxide and hydrogen is liberated.
Fatty acids refer here to carboxylic acids of biological origin, having carbon
numbers higher than CI.
Fatty acid esters refer here to triglycerides, fatty acid alkyl esters, esters of fatty
acids with fatty alcohols, and natural waxes, all being of biological origin.
In this context, the term polyol refers to alcohols having two or more hydroxy!
groups.
Here, hydrodeoxygenation (HDO) refers to oxygen removal from a compound by
means of hydrogen. Water is liberated in the reaction, and simultaneously olefinic
double bonds are hydrogenated and any sulfur and nitrogen compounds are

removed. Reactions of the HDO step are exothermal. After the HDO step, the
structure of the starting material has become paraffinic.
In this context, isomerization refers both to the isomerization of carboxylic acids
and alkykl esters thereof, and to hydroisomerization.
Isomerization of unsaturated carboxylic acids or alkyl esters of carboxylic acids,
particularly fatty acids or fatty acid alkyl esters refers here to their conversion to
branched compounds without altering their carbon number.
Hydroisomerization refers here to the isomerization of linear paraffins to give
branched paraffins.
In this context, carbon number range refers to the difference of the carbon
numbers of the largest and the smallest molecules, plus one, in the final product.
In this context, pressures are gauge pressures relative to normal atmospheric
pressure.
Classification of the Periodic System of the Elements is the IUPAC classification.
The invention is now illustrated with the appended figures 1 and 2 without
wishing to limit the scope of the invention to the embodiments of said figures.
BRIEF DESCRIPTION OF ACCOMPANYING DRAWINGS
Figure 1 shows schematically a preferable embodiment of the invention for a
process wherein the ketonisation is carried out prior to hydrodeoxygenation and
isomerization.

Figure 2 shows schematically another preferable embodiment of the invention for
a process wherein fatty acids are isomerized prior to the ketonisation and
hydrodeoxygenation steps.
In figure 1, at least one of the following starting materials is introduced to the feed
tank 30 either as separate components or as mixtures: fatty acids 4, fatty acid
esters 9, aldehydes 5, alcohols 6 or acid anhydrides 7, and dicarboxylic acid feed
3 or polyols 13 is introduced as optional additional feedstock. Part of the lighter
recirculated product fraction (for instance 102) or another hydrocarbon stream 201
may be optionally added to the feed tank 30 as a diluent. The diluent stream 202
comprises the recirculated stream 102 or hydrocarbon stream 201 or a mixture
thereof. From the feed tank 30, the feedstock stream 31 and hydrogen stream 105
are passed to an optional prehydrogenation reactor 40, followed by the passing of
the prehydrogenated stream 41 to the ketonisation reactor 50, optionally also
receiving the diluent 202. From the ketonization reactor 50, the ketone product 51
and hydrogen stream 105 are passed to the hydrodeoxygenation reactor 60,
optionally also receiving the diluent 202. The paraffinic product 61 from the
hydrodeoxygenation reactor 60 is passed to stripping 70 where unwanted
impurities are removed. Thereafter, the paraffinic product stream 71 and hydrogen
stream 105 are passed to hydroisomerization reactor 80, optionally also receiving
additional paraffinic feedstocks such as slack wax and Fisher-Tropsch waxes or
waxes produced by gasification of biomaterial (biomaterial to liquids, BTL) 8,
and the diluent 202. Following hydroisomerization 80, branched paraffins 81 may
be subjected to optional hydrofinishing 90 using a hydrogen stream 105, followed
by passing the product as the stream 91 to a distillation and separation unit 100.
Branched paraffins 82 may optionally be passed from the hydroisomerization
reactor 80 to dewaxing 110 wherein linear paraffins are removed either with
solvents or catalytically in a known manner. Separated linear paraffins may be
recirculated as stream 111 to the hydroisomerization reactor 80 for paraffins,
while branched paraffins are passed as the stream 112 to the hydrofinishing
reactor 90. In the distillation and/or separation unit 110, product components

boiling at different temperature ranges and/or for special applications; gasses 104,
gasoline 101, diesel 102, and base oil 103, are separated.
In figure 2, the unsaturated free fatty acid 3 and fatty acid alkyl ester feed 21 are
introduced into the feed tank 30 as separate components or as mixtures. Part of the
lighter product fraction to be recirculated (for instance 102) or another
hydrocarbon 201 may be optionally passed to the feed tank 30 as a diluent. The
diluent stream 202 comprises the recirculated stream 102 or hydrocarbon stream
201 or a mixture thereof. From the feed tank 30, the feedstock stream 31
containing fatty acids and/or fatty acid alkyl esters is passed to the isomerization
reactor 40 for branching the components. Following isomerization, but prior to
ketonisation, an optional prehydrogenation may be performed wherein branched
fatty acid and/or fatty acids alkyl ester components are passed as the stream 41 to
the double-bond prehydrogenation reactor 50 also receiving the hydrogen stream
6 and the optional diluent 202. Thereafter the fully saturated branched fatty acid
and/or fatty acid alkyl ester feedstock 51 is introduced to the ketonization reactor
60 optionally also receiving the dicarboxylic acid feed 5, and the optional diluent
202. Following ketonization 60, the ketone product 61 and hydrogen stream 6 are
passed to hydrodeoxygenation reactor 70 optionally also receiving the diluent
202. Following hydrodeoxygenation 70, the branched paraffinic product stream
71 and hydrogen stream 6 may be optionally passed to hydrofinishing 80. From
the hydrofinishing reactor 80, the branched paraffinic product obtained is passed
as the stream 81 to a distillation and separation unit 90 wherein product
components boiling at different temperature ranges and/or for special
applications; gas 100, diesel 102, and base oil 103, are separated.
Detailed description of the invention
It was now surprisingly found that branched saturated hydrocarbon components,
suitable as high-quality base oils, not containing heteroatoms may be obtained by
the process of the invention. Feed selected from carboxylic acids and/or

derivatives thereof, preferably fatty acids, esters of fatty acids, fatty alcohols, fatty
aldehydes, anhydrides of fatty acids, and metal salts of fatty acids of biological or
synthetic origin, or combinations thereof may be used in the process. In the
process of the invention, ketonisation, hydrogenation, and isomerization reactions
are utilized. Branched saturated hydrocarbon components are obtained as the
product.
In the ketonisation reaction the length of the hydrocarbon chain of the feedstock is
increased to such that only carbon-carbon bonds are left in the basic structure of
the molecule. Such a ketone is not suitable as base oil. The oxygen present in the
ketone group must be removed, and the low temperature properties must be
improved for instance by making short branches to the molecular structure.
In the process of the invention, the feedstock is subjected to ketonisation,
hydrodeoxygenation, and isomerization. In case unsaturated carboxylic acids
and/or esters of unsaturated carboxylic acids, preferably fatty acids and/or fatty
acid alkyl esters are used as the feedstock, the isomerization may be performed
prior to ketonisation followed by hydrodeoxygenation, otherwise the
isomerization is carried out after ketonization and hydrodeoxygenation steps.
Feed selected from the group consisting of carboxylic acids and derivatives
thereof, preferably fatty acids, esters of fatty acids, fatty alcohols, fatty aldehydes,
anhydrides of fatty acids, or metal salts of fatty acids, of biological origin, or
combinations thereof is ketonised in the process. By this means the hydrocarbon
chain length of the feedstock may be increased, and it preferably reaches the
carbon number of the base oil. In the ketonisation step one may also utilize
feedstocks that are different than those based on fatty acids. Such components are
for example dicarboxylic acids or polyols. These feedstocks are ketonised at all
the functional groups, thus increasing the molecular mass of the product compared
to ketones formed of only two fatty acids. In this case, a polyketone molecule is
formed, said polyketone being treated in a similar manner as monoketones. If

necessary, the biological starting material may be subjected to one or more
pretreatment or purification steps of the prior art for preparation of the feedstock
before ketonisation reaction.
In the hydrodeoxygenation step of the process of the invention, the ketone is
treated with hydrogen to give paraffins. The oxygen present in the ketone is
liberated as water, and any other oxygen, nitrogen, and sulfur containing
compounds are hydrogenated to paraffins, too. In addition, olefinic bonds are
hydrogenated. After hydrodeoxygenation light hydrocarbons are removed as
gases.
The hydrocarbon component obtained from the hydrodeoxygenation step may be
subjected to hydroisomerization giving branched hydrocarbon chains. Following
hydroisomerization step, the oxidation stability of the product may be improved
using an optional finishing treatment. In addition, an optional dewaxing may be
performed prior to or after the finishing.
In case unsaturated carboxylic acids or esters such as fatty acids and/or fatty acid
alkyl esters are used as the feedstock, the isomerization may be carried out prior
to ketonization, followed then by ketonization of the isomerized product, and the
HDO step is performed as the last step of the process. In said isomerization,
branches are formed in the structure of the compound, thus giving a mixture of
isomerized components. Dimers, and to a lesser extent trimers of the feedstock
components are obtained as by-products.
The steps of the process of the invention are preferably carried out in the order of
ketonisation, hydrodeoxygenation, and as the last step isomerization.
The process may also be used for processing of mixtures feeds originating from
biological starting materials and synthetic feedstocks, in which case additional
synthetic feedstocks, or feedstocks produced with other processes may be used.

Also pure synthetic feedstocks may be used, but then the products are not based
on renewable natural resources. In the processing, in addition to paraffins of
biological origin such as paraffins obtained in the process of invention or BTL
paraffins produced in processes of biomaterial gasification, also Fischer-Tropsch
waxes and/or Slack waxes obtained from crude oil by solvent dewaxing may be
used as additional feedstocks in hydroisomerization. Of synthetic processes, the
oxo-process and Fischer-Tropsch synthesis are stages in known processes for
producing liquid products from starting materials containing carbon and
hydrogen, such as from coal or natural gas.
Feedstock
The feed comprises at least one component selected from triglycerides, carboxylic
acids having a carbon number C1-C38, esters of C1-C38 carboxylic acids with C-
C11 alcohols, C1-C38 alcohols, C1-C38 aldehydes, C1-C38 carboxylic acid
anhydrides, and metal salts of C1-C38 carboxylic acids. Preferable feedstocks are
C4-C24 fatty acids of biological origin, and/or the derivatives thereof, mentioned
above, or combinations thereof. Preferable components of the feedstock are C4-
C24 fatty acids, C4-C24 fatty acid alkyl esters such as methyl esters, and esters of
fatty acids with C12-C38 alcohols having long chains, natural waxes, C4-C24
fatty alcohols reduced from fatty acids, C4-C24 aldehydes reduced from fatty
acids, C4-C24 fatty acid anhydrides, and metal salts of C4-C24 fatty acids.
Dicarboxylic acids, polyols, triglycerides, and their mixtures with the above
mentioned feedstocks may also be used as feed components.
Feed components are produced using any known methods, preferably from
starting materials of biological origin, such as materials derived from plants,
animals and fishes, selected from the group consisting of plant oils, plant waxes,
plant fats, animal oils, animal fats, animal waxes, fish oils, fish fats, fish waxes.
Corresponding starting materials derived from algae and insects are also
contemplated as well as starting materials derived from aldehydes and ketones

prepared from carbohydrates. C1-C38 and preferably C4-C24 fatty acids, or
corresponding hydroxy acids or alcohols, act as structural units in suitable starting
materials of biological origin. Since in the processing of fatty acids the service life
of the catalyst is typically short, esters and alcohols may be optionally used as
feedstocks causing less coke formation on the catalyst.
The starting materials of biological origin are suitably selected from the group
consisting of:
a) plant fats, plant oils, plant waxes, animal fats, animal oils, animal waxes, fish
fats, fish oils, fish waxes, and
b) free fatty acids or fatty acids obtained by hydrolysis, acid transesterification or
pyrolysis reactions from plant fats, plant oils, plant waxes, animal fats, animal
oils, animal waxes, fish fats, fish oils, fish waxes, and
c) esters obtained by transesterification from plant fats, plant oils, plant waxes,
animal fats, animal oils, animal waxes, fish fats, fish oils, fish waxes, and
d) fatty acid alkyl esters obtained by esterification of alcohols with fatty acids of
plant, animal and fish origin, and
e) fatty acid metal salts obtained by saponification of free fatty acids, plant fats,
plant oils, plant waxes, animal fats, animal oils, animal waxes, fish fats, fish
oils, fish waxes, and
f) alcohols and aldehydes obtained as reduction or hydrogenolysis products of
free fatty acids, or fatty acids from plant fats, plant oils, plant waxes, animal
fats, animal oils, animal waxes, fish fats, fish oils, fish waxes, and
g) fatty alcohols obtained by hydrolysis, transesterification and pyrolysis from
waxes of biological origin, and
h) anhydrides of fatty acids from plant fets, plant oils, plant waxes, animal fats,
animal oils, animal waxes, fish fats, fish oils, fish waxes, and
i) waste and recycled food grade fats and oils, and fats, oils and waxes obtained
by genetic engineering, and
j) mixtures of said starting materials.

Metal salts are alkaline earth or alkali metal salts, preferably Ca, Zn, Mg, Al, or
Na salts. Natural waxes are fatty acids esterified with alcohols having long
hydrocarbon chains. The carbon number of fatty acid and alcohol hydrocarbon
chains is typically from C12 to C38.
The starting material of biological origin may also be other than triglyceride,
ester, fatty acid, alcohol or aldehyde, or a mixture of the said starting materials if
the hydrocarbon chain length of the biological starting material is suitable or can
be processed to be suitable to the level required for diesel and base oil
applications.
If necessary, the starting material of biological origin may be pretreated or
purified by suitable known methods as described above. For instance it may be
distillated to fractions having narrower boiling ranges or carbon number
distributions or ranges. Furthermore the impurities detrimental to the properties of
the feedstock or final product may be removed by filtration through suitable
filtering aids.
In addition to compound types described above, also totally or partly synthetic
compounds, as well as mixtures of the compound types described above with
synthetic compounds are also suitable feedstocks.
Examples of suitable biological starting materials include fish oils such as baltic
herring oil, salmon oil, herring oil, tuna oil, anchovy oil, sardine oil, and mackerel
oil; plant oils such as rapeseed oil, colza oil, canola oil, tall oil, sunflower seed oil,
soybean oil, corn oil, hemp oil, olive oil, cottonseed oil, mustard oil, palm oil,
peanut oil, castor oil, jatropha seed oil, palm kernel oil, and coconut oil; and
moreover, suitable are also animal fats such as lard, tallow, and also waste and
recycled food grade fats and oils, as well as fats, waxes and oils produced by
genetic engineering. In addition to fats and oils, suitable starting materials of

biological origin include animal waxes such as bee wax, Chinese wax (insect
wax), shellac wax, and lanoline (wool wax), as well as plant waxes such as
carnauba palm wax, ouricouri palm wax, jojoba seed oil, candelilla wax, esparto
wax, Japan wax, and rice bran oil.
In the ketonization step of the process of the invention, also free carboxylic acids
or esters thereof may optionally be used as feedstocks. These linear or branched
mono and/or dicarboxylic acids may be produced by petrochemical processes or
oxo processes. Suitable monocarboxylic acids include for instance propionic,
butyric, isobutyric, 2-methyl butanoic, 2-ethyl butanoic, valeric, isovaleric,
caproic, heptanoic, caprylic, pelargonic, isononanoic, caprinic, lauric, myristic,
rnyristoleic, palmitic, palmitoleic, stearic, oleic, elaidic, linolic, linoleic,
arachidonic, behenic, and lignin acids. Suitable dibarboxylic acids include for
example the following: oxalic, malonic, succinic, glutaric, adipic, pimelic,
suberic, azelaic, and sebasic acids.
In case where alcohols are ketonised in the process of the invention, also diols
and/or polyols may be used as the feedstock in addition to fatty alcohols. Suitable
diols include for instance diols derived from dicarboxylic acids, dimers of fatty
alcohols, and 2,2-dimethyl-1,3-propanedioI (NPG). Examples of suitable
polyhydric alcohols include glycerol, 2-ethyl-2-hydroxymethyl-propane-1,3-diol
(TMP), 2-methyl-2-hydroxymethyl-propane-1,3-dioI (TME), 2-butyl-2-ethyl-
propanediol (BEPD), and 2,2-bis-(hydroxymethyl)-l,3-propanediol (PET).
Preferably alcohols containing tertiary carbons are not used when the thermal
stability of the base oil to be produced has to be good.
Feedstocks used in the isomerization of unsaturated carboxylic acids, or alkyl
esters of unsaturated carboxylic acids; particularly in the isomerization of
unsaturated fatty acids or fatty acid esters, contain at least 20 %, preferably at
least 50 %, and particularly preferably at least 80 % by weight of compounds
having double bonds. The feedstock may also be a mixture of unsaturated

carboxylic acids and unsaturated carboxylic acid alkyl esters. Typically, the
number of unsaturated bonds in compounds of the feedstock is 1 to 3. Preferably
the feedstock comprises at least 40 % by weight of monounsaturated fatty acids or
fatty acid esters, more preferably at least 70 % by weight. The feedstock may also
comprise polyunsaturated fatty acids or fatty acid esters. The presence of an
unsaturated bond in the molecule causes the formation of a cation as an
intermediate, thereby facilitating the skeletal isomerization reaction.
Hydrocarbon may optionally be added as a diluent to the feedstock and/or in
various process stages, such diluent may be for instance hydrocarbon of the
middle distillate diesel class. Boiling ranges of hydrocarbons of the diesel class
are between 150 and 400 °C, typically between 180 and 360 °C.
Process
In the process according to the invention, the feedstock is subjected to
ketonisation, hydrodeoxygenation, and isomerization.
Isomerization step of unsaturated carboxylic acids and/or esters
The isomerization may be carried out prior to the ketonisation step in case the
feedstock comprises unsaturated carboxylic acids and/or alkyl esters of
unsaturated carboxylic acids, preferably unsaturated fatty acids and/or unsaturated
fatty acid alkyl esters. Acidic catalyst materials are used as the catalysts.
Preferable the isomerization catalysts are aluminium phosphates, silica aluminium
phosphates and zeolites, the catalyst preferably being a zeolite of the pentasil or
mordenite type. The reaction temperature ranges from 150 to 350 °C, preferably
from 200 to 290 °C, the reaction pressure being between 0 and 5 MPa, preferably
between 0.1 and 2 MPa. Pressure is used to prevent lighter components from
evaporating. Water or a lower alcohol may be added to the feedstock to suppress
acid anhydride formation due to dehydration or dealcoholation. It is preferable to
add water when the feedstock comprises unsaturated fatty acids and alcohol or

when the feedstock comprises esters of unsaturated fatty acids. Typically the
amount of added water or lower alcohol is 0 - 8 %, and preferably 1-3 % by
weight based on the total reaction mixture. The lower alcohol is C1 - C5 alcohol,
and preferable alcohols are methanol, ethanol and propanol, with a greater
preference given to those having the same alkyl group as that of the starting fatty
acid ester to be isomerized. Excess water (more than 10 %) should be avoided in
order to prevent estolide formation. This skeletal isomerization step may also be
carried out in the absence of water or lower alcohol In case the reaction is
performed as a batch reaction, the amount of the catalyst ranges from 0.01 to 30
% by weight of the total reaction rnixture, preferably from 0.5 to 10 %, by weight.
In the batch reactor, the reaction time is less than 16 hours, preferably less than 8
hours, particularly preferably less than 4 hours. In case a fixed bed reactor is used,
the feed weight hourly space velocity (WHSV) is 0.1 - 100 1/h, where the amount
of the feedstock is expressed in grams per hour per grams of the catalyst.
Prehydrogenation step
The isomerized product obtained above, or the non-isomerized feedstock may be
subjected to an optional prehydrogenation prior to the ketonisation step to reduce
side reactions caused by the double bonds. Prehydrogenation is performed as a
separate process under mild conditions. Prehydrogenation is performed in the
presence of a prehydrogenation catalyst, at a temperature between 50 and 400 °C,
under a hydrogen pressure ranging from 0.1 to 20 MPa, the feed flow rate WHSV
being between 0.1 and 10 1/h, the conditions preferably comprising temperatures
between 100 and 300 °C, hydrogen pressures ranging from 1 to 15 MPa, WHSV
being from 0.5 to 5 1/h, particularly preferable conditions comprising temperatures
between 150 and 280 °C, pressures ranging from 2 to 10 MPa, WHSV being from
1 to 3 1/h. The prehydrogenation catalyst may contain metals of the Group VIII
and/or VIA of the periodic system of the elements. The prehydrogenation catalyst
is preferably a supported Pd, Pt, Ni, Ru, Rh, NiMo or CoMo catalyst, the support
being activated carbon, alumina and/or silica.

The optionally prehydrogenated product from the isomerization of fatty acids
and/or fatty acid alkyl ester, or the optionally prehydrogenated feedstock is passed
to the ketonisation step yielding as the product a ketone with an increased
hydrocarbon chain length. The obtained ketone is hydrogenated in the HDO step
to give saturated hydrocarbons.
Ketonisation step
In the ketonisation step, the pressure ranges from 0 to 10 MPa, preferably from
0.1 to 5 MPa, particularly preferably from 0.1 to 1 MPa, whereas the temperature
ranges between 100 and 500 °C, preferably between 100 and 400 °C, particularly
preferably between 300 and 400 °C, the feed flow rate WHSV being from 0.1 to
10 1/h, preferably from 0.3 to 5 1/h, particularly preferably from 0.3 to 3 1/h. In the
ketonisation step metal oxide catalysts may be used. Typical metals include Na,
Mg, K, Ca, Sc, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Y, Zr, Mo, Rh, Cd, Sn, La, Pb, Bi,
and rare earth metals. These metal oxides may be on a support, typical supports
being laterite, bauxite, titanium dioxide, silica and/or aluminium oxide. The metal
is preferably molybdenum, manganese, magnesium, iron and/or cadmium, the
support being silica and/or alumina Particularly preferably the metal is
molybdenum, manganese and/or magnesium as oxide in a catalyst without
support. No special catalysts are needed for the ketonisation of metal salts of fatty
acids (soaps), since the metal present in the soap promotes the ketonization
reaction.
Hydrodeoxygenation
In the HDO step of the invention, the ketone and hydrogen gas are reacted under a
pressure ranging between 0.1 and 20 MPa, preferably between 1 and 15 MPa,
particularly preferably from 2 to 10 MPa, the temperature being from 100 to 500
°C, preferably from 150 to 400 °C, particularly preferably from 200 to 350 °C, the
flow rate WHSV varying from 0.1 to 10 1/h, preferably from WHSV 1 to 5 1/h,
and particularly preferably from WHSV 1 to 3 1/h. In the HDO step, special
catalysts containing a metal of the Group VIII and/or VIA of the periodic system

of the elements, on a support may be used. The HDO catalyst is preferably a
supported Pd, Pt, Ni, NiMo or CoMo catalyst, the support being activated carbon,
alumina and/or silica.
In a preferable embodiment, the reaction product obtained after the HDO step is
purified for instance by stripping with steam, or with a suitable gas such as a light
hydrocarbons, nitrogen or hydrogen. It is preferable for the process to remove
impurities and water as efficiently as possible prior to the hydro isomerization
step and/or finishing step.
In case the feedstock is already subjected to the isomerization of fatty acids and/or
fatty acid alkyl esters, only optional finishing and separation steps are performed
after the HDO and the optional purification steps.
Isomerization step as hydroisomerization
In case the isomerization of carboxylic acids and/or carboxylic acid alkyl esters
was not carried out, a hydroisomerization step is carried out after the ketonisation,
HDO and optional purification steps. In this case the hydrogenated product
obtained from ketonisation followed by hydrodeoxygenation, and optional
paraffinic additional feed are passed to the hydroisomerization reactor to react
with hydrogen gas in the presence of a isomerization catalyst. In the
hydroisomerization step, the pressure ranges from 0 to 20 MPa, preferably from 1
to 15 MPa, and particularly preferably from 4 to 10 MPa. The temperature ranges
between 100 and 500 °C, preferably between 200 and 400 °C, and particularly
between 250 and 370 °C. The flow rate WHSV in between 0.1 and 10 1/h,
preferably between 1 to 5 1/h, and particularly preferably between 1 and 3 1/h. In
the hydroisomerization step, special isomerization catalysts containing molecular
sieves and metals of the Group VIII of the periodic system of the elements, for
instance Ni, Pt, and Pd, may be used. Alumina and/or silica may be used as
supports.

Dewaxing step
Following ketonisation, HDO and hydroisomerization steps of the feedstock, an
optional dewaxing may be performed either catalytically or as solvent-based
dewaxing. An optional dewaxing may also be carried out after the isomerization,
ketonisation and HDO steps of unsaturated fatty acid and/or fatty acid alkyl ester
feedstock.
In the catalytic dewaxing, hydrogen gas and the hydrogenated component, as well
as the optional paraffinic additional feed react in the presence of a dewaxing
catalyst. Zeolite catalysts comprising metals of the Group VIII of the periodic
system of the elements such as Ni, Pt or Pd are used as dewaxing catalysts. In the
dewaxing step, the pressure varies from 0.1 to 20 MPa, the temperature being
between 100 and 500 °C.
In the solvent-based dewaxing, linear paraffinic waxes are separated by dissolving
the oil (hydrocarbon product) in a mixture of solvents, for instance methylethyl
ketone and toluene. In the process, the solvent and the feed are passed in counter
current manner and thus mixed. The mixture of oil and solvent is introduced to a
cooling unit. Cooling results in the crystallization of the linear paraffinic waxes,
whereas branched paraffins remain as oily liquids. The temperature used depends
on the target low temperature properties of the product, the pour point of the final
product decreasing as the temperature in dewaxing is decreased. Wax crystals are
filtered from the mixture, collected for further processing, and the solvent is
separated by evaporation from the base oil. Solvent-based dewaxing is also
suitable for fatty acids and/or fatty acid alkyl esters after isomerization and
prehydrogenation of the double bonds. Linear fatty acids and/or linear fatty acid
alkyl esters are thus separated from the mixture of branched and non-crystallizable
compounds by dissolving the feed for instance in hexane, and cooling as
described above.
Finishing step

The above obtained and optionally dewaxed product may optionally be finished
for removing any double bonds and aromatics. In hydrofinishing, the finishing is
performed using hydrogen in the presence of a catalyst, the pressure ranging from
1 to 20 MPa, preferably from 2 to 15 MPa, and particularly preferably from 3 to
10 MPa, and the temperature ranges between 50 and 500 °C, preferably between
200 and 400 °C, and particularly preferably between 200 and 300 °C. In the
hydrofinishing, special catalysts containing metals of the Group VIII of the
periodic system of the elements, and a support may be used. The hydrofinishing
catalyst is preferably a supported Pd, Pt, or Ni catalyst, the support being alumina
and/or silica. Finishing may also be achieved by removing polar components
using adsorption materials, such as clay or molecular sieves.
Following optional finishing, the product is passed to a distillation and/or
separation unit in which product components boiling over different temperature
range and/or product components intended for different applications are separated
from each other.
If desired, the hydrocarbon component obtained as the product, or another suitable
hydrocarbon may be used as a diluent in various stages of the process of the
invention, such as in the ketonization, HDO and/or isomerization steps for
increasing the conversion and/or selectivity and/or for controlling the exothermal
nature of the reactions.
A fixed bed reactor, for instance the trickle bed reactor of the prior art is
preferably used in prehydrogenation, HDO, hydroisomerization, and
hydrofinishing steps.
Product
The process according to the invention yields a high quality branched and
paraffinic hydrocarbon component suitable as a base oil or base oil component.
The base oil product has excellent viscosity and low temperature properties. The

process according to the invention also yields typically as a by-product a branched
and paraffinic hydrocarbon product suitable for diesel fuel pool. The diesel
component contains typically some short carbon-carbon side branches, resulting
in an exceptionally low cloud point and cold filter plugging point but still a good
cetane number. In addition, a hydrocarbon component suitable to be used as a
solvent, gasoline and/or a component of gasoline is obtained as a by-product. All
products are preferably of biological origin.
A branched, saturated and paraffinic hydrocarbon component is the main product
in the process according to the invention, particularly when the ketonisation and
hydrodeoxygenation steps are carried out prior to isomerization. A branched,
saturated and paraffinic hydrocarbon component containing high amounts of
cycloparaffins is obtained when carboxylic (fatty) acids are isomerized prior to the
ketonisation and hydrodeoxygenation steps.
Feedstocks, which are preferably derived from biological starting materials, have
a substantial effect on the composition and distillation range of the product. For
instance feedstocks consisting of fatty acids may be fractionated by distillation to
give narrow fractions to be tailored for various applications. For feedstocks
having hydrocarbon chains of C16, C18, C20 and C22, typical carbon numbers of
products are respectively C31, C35, C39, and C43. Narrow product fractions are
obtained since the distillation range of the product mainly depends on the length
of the hydrocarbon chain of the feedstock. Base oils with narrow distillation
ranges obtained according to the invention have extremely low volatilities when
compared to corresponding products of the prior art.
Carbon number range of the base oil of the invention is extremely narrow,
typically no more than 5 carbons wide. Most typical structures and carbon number
ranges (C31-C35) of the base oils 1 and 2 produced by the process of the
invention (4-6 cSt/100 °C) are presented in Table 2. Carbon number depends on

the carbon number of the feedstock. Most typical carbon numbers are shown bold-
faced

Base oils of biological origin shown in Table 2 are produced as follows:
1. Stearic acid fraction is ketonised, hydrodeoxygenated, and hydroisomerized.
2. Unsaturated fatty acid is isomerized, ketonised, and hydrodeoxygenated.
Using feedstocks with different hydrocarbon chains, the molecular masses of the
products may be increased to reach viscosity ranges required for different
applications by means of the ketonisation reaction. With the process of the
invention, lighter hydrocarbon products such as solvents, gasoline, and diesel
fuels may be produced from feedstocks of shorter hydrocarbon chains.
Saturated hydrocarbons are classified according to the carbon and hydrogen atoms
by field ionization mass spectrometry (FIMS) method as follows:


In Tables 2 and 3, the percentages (%, by FIMS) refer to the groups of compounds
determined according to said method.
In Table 3 are presented typical carbon number ranges (C25-C35) and
compositions of synthetic (GTL) and mineral oil (VHVI and Slack Wax) base
oils, belonging to the same viscosity class of about 4 - 6 cSt measured at 100 °C.
Structures of naphthenes are examples of different compound types. The average
carbon numbers are shown bold-faced.
Products shown in Table 3 are produced as follows:
1. GTL is a hydroisomerized Fischer-Tropsch waxy fraction derived from
natural gas
2. Slack Wax is a hydroisomerized Slack Wax fraction derived from crude oil
3. VHVI is a hydrocracked and hydroisomerized base oil derived from crude oil



With respect to carbon number and molecular structure, base oils of the invention
differ from products of the prior art, as may be clearly seen from Tables 2 and 3.
In case the isomerization is based on the double bonds of C18 fatty acid skeleton
(structure 2 in Table 1), the structure of the branched, saturated hydrocarbon
product obtained using the process according to the invention is different from the
one obtained for example when hydroisomerizing C25-C35 paraffins in Slack and
GTL waxes. In the present case the branches are mainly in the middle of the long
hydrocarbon chain, due to the common ω9 olefrnic unsaturation positions
responsible of branching. In Slack and GTL waxes (structures 1 and 2 in Table 3),

the branches are mainly near the ends of the hydrocarbon main chain. There are
typically alkyl branches having carbon numbers 1 - 4 within the hydrocarbon
chain of the product. With respect to the branching site, the branched components
are mixtures of different isomers. Branches more in the middle of the hydrocarbon
chain lower the pour point considerably more than those at the ends of the chain.
In addition to the location of the branches, also the number of branches affects the
pour point. The pour point being lowered by increasing number of branches, but
at the same time also the viscosity index is reduced. It is known that an optimum
correlation between the viscosity index and pour point is attained with only few
branches present in the main hydrocarbon chain. In the process of the invention
where the isomerization is based on the double bonds of C18 fatty acid skeleton,
the number of branches is limited by the number of double bonds in the feedstock,
and thus the base oil may not be branched too much to cause the VI to be reduced
near the lower limit. In a similar manner, lowering of the pour point is limited by
the number of double bonds in the feedstock.
In case the isomerization is based on hydroisomerization, such as of the
C31/C33/C35 wax of hydrodeoxygenated ketone (structure 1 in Table 1), the
structure of the branched, saturated hydrocarbon product obtained using the
process according to the invention resembles to the one obtained
hydroisomerizing C25-C35 paraffins in SW and GTL wax. In both present cases
of the invention, the length of the hydrocarbon chain is though higher, typically
from C31 to C35 and narrower than those of technically known base oils. Due to
relatively long hydrocarbon main chain and controlled level of branching, the
viscosity and cold properties of the product of invention are very good: the
kinematic viscosity (KV100) is about 5 cSt and VI above 150 even though pour
point is decreased to near -20 °C.
Naphthenes of the final product of the invention are mononaphthenes and non-
fused dinaphthenes. In the Slack wax and VHVI products of the prior art, the

dinaphthenes are mainly fused. The VI of fused naphthenes is poorer than that of
non-fused naphthenes. In addition, it is known that the non-fused naphthene rings
are desirable as components of base oils since their VI is reasonably high but the
pour point low. In the VHVI products of the prior art (structure 3 in Table 3), in
addition to mononaphthenes there are polycyclic naphthenes with 3-5 rings
typically not present in the product of the invention. These are formed as a result
of cracking and hydrogenation of naphthenes and aromatic compounds of the
mineral crude oil based feed.
In addition to pour point and viscosity index, the relationship of isoparaffins and
1-2 ring naphthenes to 3-6 ring naphthenes seem to play the major role in cold
cranking. If too high amount of multiring naphthenes are present, they give higher
CCS-30 values since they are present as an extremely viscous liquid. Furthermore,
if normal paraffins are present after hydroisomerization, they give high CCS-30
values by crystallization and thus inhibiting the liquid to flow,
The base oil of biological origin according to the invention comprises a product
produced from starting materials of biological origin. The base oil comprises
branched hydrocarbons having carbon number at least C18. Said product contains
not more than 20 %, preferably not more than 10 %, and particularly preferably
not more than 5 %, by weight, and at best not more than 1 % by weight of linear
paraffins, and at least 90 %, preferably at least 95 %, and particularly preferably at
least 97 %, by weight, and at best 99 % by weight of saturated hydrocarbons.
Base oils of the invention comprise mono and dinaphthenes, but no polycyclic
naphthenes, the dinaphthenes thereof being non-fused. Based on the FIMS
analysis, the product of the invention contains mononaphthenes more than 5 %,
preferably 5-20 %, particularly preferably 5- 15 %, and at best 5- 10 %; and less
than 1.0 %, preferably less than 0.5 %, and particularly preferably less than 0.1 %
of polycyclic naphthenes measured by FIMS.

For base oils of the invention, having kinematic viscosity KV100 of 4 - 7 mm2/s,
the viscosity index is at least 115 and preferably at least 120, particularly
preferably at least 150, and at best at least 160 (ASTM D 2270) and pour point
lower than -9 °C, preferably lower than -12 °C and particularly preferably lower
than -15 °C (ASTM D 97 / 5950).
Low temperature dynamic viscosity, CCS-30, for base oil is no more than
29.797*(KV100)2,7848 cP, preferably no more than 34.066*(KV100)2.3967 cP; CCS-
35 is no more than 36.108*(KV100)3,069 cP, preferably no more than
50.501 *(KV100)2,4918 cP measured by method ASTM D 5293; pour point being
not over -9 °C, preferably not over -12 °C and particularly preferably not over -15
°C (ASTM D 97 / 5950).
For base oil of the invention the volatility of product, having KV100 from 3 cSt to
8 cSt, is no more than 2271.2*(KV100)-3,5373 % by weight as determined by the
method of DIN 51581-2 (Mathematical Noack method based on ASTM D 2887
GC distillation).
Width of the carbon number range of base oils of the invention is no more than 9
carbons, preferably no more than 7 carbons, particularly preferably no more than
5 carbons, and at best 3 carbons (FIMS). More than about 50 %, preferably more
than 75 % and particularly preferably more than 90 % by weight of the base oil
contain hydrocarbons belonging to this narrow carbon number range.
Distillation range of base oils of the invention is no more than 155 °C, preferably
no more than 100 °C, particularly preferably no more than 70 °C, and at best no
more than 50 °C (determined by the method of ASTM D 2887, distillation points
D10 and D90).
Sulfur content of said base oil of the invention is less than 300 ppm, preferably
less than 50 ppm, and particularly preferably less than 1 ppm, (ASTM D 3120).

Nitrogen content of said base oil of the invention is less than 100 ppm, preferably
less than 10 ppm, and particularly preferably less than 1 ppm, (ASTM D 4629).
Base oils of the invention, based on biological starting materials, contain carbon
14C isotope, which may be considered as an indication of the use of renewable raw
materials. Typical 14C isotope content (proportion) of the total carbon content in
the product, which is completely of biological origin, is at least 100 %. Carbon
14C isotope content is determined on the basis of radioactive carbon (carbon 14C
isotope) content in the atmosphere in 1950 (ASTM D 6866). 14C isotope content
of the base oil according to the invention is lower in cases where other
components besides biological components are used in the processing of the
product, said proportion being, however, more than 50 %, preferably more than 90
%, particularly preferably more than 99 %. In this way, even low amounts of base
oil of biological origin may be detected in other types of hydrocarbon base oils.
The cetane number of the diesel product obtained with the process of the
invention, is more than 40, preferably more than 55, and particularly preferably
more than 70. It contains more than 60 %, preferably more than 99 % by volume,
of paraffins, and less than 30 %, preferably less than 1 % by volume, of aromatics,
based on the IP-391 method. The product comprises less than 40 %, preferably
less than 10 %, by weight, of linear n-paraffms. The cloud point of the diesel
component is less than 0 °C, preferably less than -15 °C, and particularly less than
-30 °C. Typically, the diesel product obtained is totally of biological origin. In the
product of the invention, there are branches formed by carbon-carbon bonds, this
structure resulting in a very low cloud point.
Advantages of the invention
The process of the invention allows particularly for the use of renewable starting
materials of biological origin, containing heteroatoms, for producing base oils, but
also diesel and gasoline components. In addition to traditional crude oil, a

completely new raw material source for high-quality branched paraffinic base oils
is provided according to the invention. Also carbon dioxide emissions
contributing to the greenhouse effect may be reduced by using renewable raw
material sources instead of non-renewable ones.
According to the process of the invention, base oil containing only carbon and
hydrogen is obtained, the stability of said base oil in humid conditions being
higher than that of esters or other base oils containing heteroatoms. A paraffinic
hydrocarbon component is not decomposed as easily as esters that form corrosive
acids. A nonpolar and fully saturated hydrocarbon component free of sulfur is
obtained using the process of the invention by removing oxygen of ketones, and
the heteroatoms of any impurities of the feedstock in the HDO step. In the
isomerization step, the carbon chain is branched, thus improving low temperature
properties, that is, the pour point is lowered, low-temperature fluidity enhanced
and filterability at low temperatures is improved. Solid wax is converted to oily
hydrocarbon having viscosity index (viscosity-temperature-dependence) very
suitable for top-tier base oils without blending limitations, and further, it is
compatible with lubricant additives.
With the process of the invention, high-quality saturated base oil having a low
pour point may be produced, said base oil being also very useful at low
temperature conditions. The product is typically free of sulfur, the viscosity index
thereof being preferably at least 120, and thus it may also be suitably used in
applications of Group HI base oils.
Composition, properties and boiling range of the product are also strongly
influenced by the starting material of biological origin. The starting material may
be distilled to fractions according to carbon numbers. According to the invention,
branched paraffinic base oil having narrow boiling ranges and different physical
properties may be processed from these fractions. Typical carbon number ranges
of the product components are as follows: gas C1-C4, gasoline C5-C10, diesel

C11-C26, and base oil having carbon number of at least C18. Distillation range of
base oil produced from a feedstock having a single carbon number is the
narrowest.
Narrow distillation range indicates that the product does not contain initial light
fraction, meaning molecules considerably lighter than the average, which can be
seen as decreased volatility of the product, resulting in reduced emissions and
reduced use of lubricants in practical applications. The "tail" composed of the
heavier components, meaning molecules considerably heavier than the average, is
also missing from the product. This results in excellent low temperature properties
of the product.
For the base oil of the invention, the carbon number and distillation range are
governed by the feedstock composition. For base oils of the prior art, the
distillation range is adjusted by distilling the product to obtain a fraction having
the desired kinematic viscosity. It is preferable that lubricants have base oils with
narrow carbon number distribution and thus narrow distillation range, so that
lubricating oils contain molecules of similar sizes behaving in a similar way under
different conditions.
The base oil according to the invention has high viscosity index, which leads to a
significantly decreased need of high price Viscosity Index Improver (VII) or in
other terms Viscosity Modifier (VM). It is commonly known, that the VII is an
additive, which causes highest amount of deposits in vehicle engines. In addition,
reduction of the amounts of VII results in significant savings in costs.
Also, because the base oil is non-toxic, contains no sulfur, nitrogen or aromatic
compounds typically present in the conventional mineral oil based products, it
may more safely be used in applications where the end user is exposed to oil or oil
spray.

Moreover, response of the base oil according to the invention is extremely high
for antioxidants and pour point depressants, and thus the life time of the
lubricating oils are longer and they can be used in the colder environment than
lubricants based on the conventional base oils.
Even though the branched, saturated hydrocarbon product is produced from
saturated and unsaturated natural fatty acids, it contains no oxygen, and thus its
hydro lytic stability is much higher than that of synthetic ester base oils. Due to the
lack of ester bonds, also the formation of acidic degradation products is
minimized. In addition, the oxidation stability of the saturated base oil is higher
than that of ester base oil containing unsaturated fatty acid structural units.
Compared to esters, the base oil of the invention is more compatible with
conventional base oils derived from crude oil, base oils obtained from Fischer-
Tropsch process, and with hydrocarbon base oils, as well with lubricant additives.
Moreover, it is compatible with elastomers, and thus it can be used in modern
vehicle engines without modifications.
An additional advantage of the base oil according to this invention is that it fulfils
the API group III base oil specifications. Therefore it can be used in engine oil
formulations like other group III base oils according the same interchanging rules
without need to perform new engine tests.
The base oil of the invention is preferably based on renewable natural resources.
Starting materials of the process of the invention are available all over the world,
and moreover, the utilization of the process is not limited by significant initial
investments in contrast for instance to the GTL technology.
The products of the inventive process are carbon dioxide neutral with respect to
the use and disposal thereof, that is, they will not increase the carbon dioxide load
of the atmosphere in contrast to products derived from fossil starting materials.

Further advantages of the invention relate to diesel fuel component of biological
origin, which has excellent low temperature properties and cetane number
compared to those of solutions of the prior art, where components based on fatty
acid methyl esters are used. Problems associated with low temperature properties
have been avoided by isomerizing waxy n-paraffms derived from fatty acids to
give isoparaffins.
The middle distillate diesel fuel component obtained is a high-quality
hydrocarbon component of biological origin particularly suitable as a component
for diesel fuel, as isoparaffinic solvent, and as lamp oil, the cetane number thereof
being even above 70, the cloud point being as low as below -30 °C. Fouling of the
engine may be expected to be reduced in comparison to fuels of biological origin
already known in the art, said fuels containing incompletely burning ester
components. Moreover, the density of the composition is lower. The composition
requires no changes of the automobile technology or logistics. Higher energy
content of the biological component per unit volume compared to products based
on esters may also be mentioned as an advantage.
With the optional prehydrogenation step side reactions of double bonds of
hydrocarbon chains may be reduced. Side reactions, such as polymerization, ring
formation and aromatization cause coke formation on the catalyst, thus reducing
its service life. Ring formation and polymerization change also viscosity
properties of the hydrocarbon components. Moreover, said prehydrogenation
results in improved yields of the final base oil product.
In addition to hydrocarbon chain lengthening also oxygen may be removed from
the feedstock as carbon dioxide with the ketonization reaction, which is favorable
for the process to minimize hydrogen consumption. With the isomerization, low
temperature properties of the product may be improved without interfering with
viscosity properties.

With the solution of the invention, high hydrogen partial pressure may be
maintained throughout the whole process, and keep levels of impurities low.
Carbon monoxide, carbon dioxide and water contents may be lowered to such an
extent that light stripping in the HDO stage or in a separate gas/liquid separation
vessel is sufficient to remove residual impurities prior to isomerization.
Advantages of the invention also include protection of the isomerization catalyst,
thus preventing the deactivation thereof.
The properties of the hydrocarbon components produced with the process
according to the invention are excellent, and moreover, distillation ranges of
products produced from fatty acids with a specific carbon number are
considerably narrower that those of VHVI base oils. The products are well suited
as base oils without blending limitations, and further, the products are also
compatible with lubricant additives.
Examples
The invention is now illustrated by means of the following examples without
wishing to limit the scope of the invention thereby. Properties of the hydrocarbon
components prepared in the examples are presented in Table 4. Similarly,
properties of some of the base oils of the prior art are shown in Table 5. It is
however clear that the invention is not limited to embodiments described in the
examples.
Example 1
Preparation of a hydrocarbon component from stearic acid fraction
(C17H35COOH)

A mixture of plant oils (linseed, soybean, and rapeseed oils) was pretreated by
hydrolysis and distillation to obtain fatty acid fractions according to carbon
numbers. The C18 acid fraction thus obtained was used as the feed, the fraction
being diluted with a paraffinic diesel fuel of biological origin. C18 acid content of
the feedstock thus obtained was 31 %, by weight Double bonds of the feedstock
were selectively prehydrogenated, and the stearic acid was continuously ketonised
at atmospheric pressure, in a tubular reactor using a MnO2 catalyst. Temperature
of the reactor was 370 °C, the WHSV of total feed being 3 1/h. 22 % by weight of
18-pentatriacontanone, or stearone, in a diluent was obtained as the ketonisation
product.
In the next step, the stearone/diluent mixture obtained above was
hydrodeoxygenated in a high pressure Parr reactor using a dried and activated
NiMo/Al2O3 catalyst, to give linear paraffins. The ketone was hydrogenated at
330 °C, under a pressure of 5 MPa, mixing at 300 rpm until no ketone peak was
detected in the FTTR spectrum. 71 % by weight of linear C35 paraffin was
obtained from stearic acid.
The paraffin wax obtained above was isomerized in a Parr reactor to give a
branched paraffin of the base oil class using a reduced Pt molecular sieve/Al2O3
catalyst. Preheated mixture of the paraffin/diluent was isomerized under a
hydrogen pressure of 3 MPa and at 340 °C until a pour point of -6 °C was
obtained. Finally, light fractions were distilled from the product at reduced
pressure, followed by finishing of the paraffinic product by filtering through
kieselguhr. Hydrocarbon components may be produced in a similar way from
other fatty acids and dicarboxylic acids.
Example 2
Preparation of a hydrocarbon component from fatty acids derived from palm oil

Palm oil was hydrolyzed. Fatty acids derived from palm oil were used as the
feedstock following selective prehydrogenation of the double bonds of said fatty
acids. After hydrogenation, the fatty acid composition was as follows: C14 1 %,
C16 44 %, C18 54 %, and C20 1 %, all percentages being by weight. The fatty
acids were ketonised as in Example 1. Following ketonization, the solvent was
distilled off, yielding a product with the following composition: C15COC15
ketone, 10.4 %, C15COC17 ketone, 42.1 %, and C17COC17 ketone, 43.6 %, by
weight.
The ketone mixture obtained from the ketonisation stage was hydrodeoxygenated
in a Parr reactor using a dried and activated N1Mo/Al2O3 catalyst to give linear
paraffins. Hydrodeoxygenation was carried out under a pressure of 3.3 MPa, at
330 °C, mixing at 300 rpm. Linear paraffin with the composition: C33 chain 41.8
%, C34 chain 2.1 %, and C35 chain 43.8 % by weight was obtained from palm
oil.
The linear paraffin wax obtained in the HDO step was isomerized in a Parr reactor
to give branched paraffins of the base oil class using a reduced Pt molecular
sieve/Al2O3 catalyst. Isomerization was performed at 340 °C, under a hydrogen
pressure of 3 MPa until the pour point of the product was below -15 °C. Finally,
light fractions were distilled off under reduced pressure.
Palm oil also contains C16 and C18 fatty acids, the hydrocarbon component thus
having a wider distillation range and a lower kinematic viscosity compared to the
product of Example 1. Hydrocarbon components may also be produced in a
similar way from other plant and fish oils, and animal fats.
Example 3
Preparation of a hydrocarbon component from methyl esters of fatty acids derived
from animal fats

Purified animal fat was transesterified under basic conditions with methanol at 70
°C, under a pressure of 0.1 MPa, in the presence of a sodium methoxide catalyst
in two steps, thus producing methyl esters of fatty acids. The reaction mixture was
purified by washing with acid and water, and the mixture of fatty acid methyl
esters was dried The fatty acid composition of the mixture of methyl esters
derived from animal fat was as follows: C14:0 2 %; C16:0 23 %, C16:l 3 %,
C18r0 13 %, C18:l 40 %, C18:2 11 %, C18:3 1 % by weight.
The mixture of fatty acid methyl esters obtained above was used as the feedstock
of the process, diluted with paraffinic diesel of biological origin. The fatty acid
methyl ester content of the feedstock was 30 % by weight, the feedstock being
continuously ketonised in a tubular reaction as described in Example 1. Both
saturated and unsaturated ketones were obtained as the product. Their carbon
numbers were as follows: 10 % of C21-C28 ketones, 3 % of C29 ketone, 10 % of
C31 ketone, 33 % of C33 ketone, and 20 % by weight of C35 ketone.
The ketone mixture was first hydrodeoxygenated a Parr reactor as described in
Example 2, followed by isomerization according to Example 2. Hydrocarbon
components may also be produced in a similar manner from methyl esters derived
from plant and fish oils. Service life of the ketonization catalyst may be extended
by using less corrosive methyl esters instead of fatty acids.
Example 4
Preparation of a hydrocarbon component from metal stearates
A metal stearate (CH3(CH2)16COO)2Mg was ketonised under atmospheric
pressure in a Parr reactor at 340 °C and with mixing rate of 300 rpm. Stearone, or
C35 ketone, obtained as the product was hydrodeoxygenated and isomerized as
described in Example 1. The product thus obtained correspond the product of
Example 1. Hydrocarbon components may also be produced in a similar manner
from other metal salts of fatty acids derived from plant oils, animal fats and fish

oils, as well as from metal salts of fatty acids obtained by saponification of plant
and fish oils or animal fats. No special catalyst is needed for the ketonization in
case metal salts are used.
Example 5
Preparation of a hydrocarbon component from carboxylic acids of tall oil
Distilled tall oil fatty acids were isomerized in a Parr high-pressure reactor with
mordenite type zeolite. Tall oil fatty acids, 5 wt-% of the catalyst and 3 wt-% of
water, calculated of total reaction mixture, were placed in a reactor and air was
removed from the autoclave with purging nitrogen. The mixture was stirred with
300 rpra The reactor was heated to 280 °C and kept under nitrogen atmosphere of
1.8 MPa for 6 hours. After cooling, the reaction mixture obtained was taken from
the autoclave, and the zeolite was filtered off. The filtrate was distilled under
reduced pressure to yield monomelic acids.
The monomelic acids thus obtained were placed in an autoclave, and double
bonds were hydrogenated at 150 °C with a catalyst containing 5 wt-% Pd on
carbon under hydrogen atmosphere of 2 MPa until the reaction was complete.
Catalyst amount was 2 wt-% of monomeric acid. Then, the reaction mixture was
cooled, and the catalyst was filtered off.
The obtained crude branched chain fatty acids were subjected to a conventional
solvent fractionation procedure to yield isomerized fatty acids. To the crude
branched chain fatty acids, about 2-fold amount by weight of hexane was added.
After this mixture was cooled to -15 °C, the resulting crystals of non-isomerized
fatty acids were filtered off. Then, the hexane was distilled off from the filtrate to
yield purified isomerized fatty acids.
The isostearic acid was diluted with a paraffinic diesel of biological origin in a
ratio of 30/70 %, by weight. The mixture thus obtained was continuously

ketonised at atmospheric pressure in a tubular reactor using a MnO2 catalyst. The
temperature of the reactor was 370 °C, the WHSV being 1.7. A mixture of
isomerized ketones was obtained as the product.
The mixture of isomerized ketones was hydrogenated in a HDO step in a Parr
reactor as in Example 2. Solvents were distilled from the final product under
reduced pressure. Thereafter, the product was subjected to solvent dewaxing to
remove linear paraffins, and finally, the paraffinic product was finished by
filtering through kieselguhr. Mainly branched paraffins were obtained as the final
product. Hydrocarbon components may also be produced in a similar way from
other isomerized fatty acids or from isomerized methyl esters of fatty acids of
plant, animal and fish origin.
Example 6
Preparation of a hydrocarbon component from tall oil fatty acids and dicarboxylic
acids
Distilled mixture of fatty acids from tall oil was isomerized and prehydrogenated
as described in Example 5. The isostearic acid fraction thus obtained and the C6
dicarboxylic acid (adipic acid) were mixed in a molar ratio of 1:3, and the mixture
was ketonised under atmospheric pressure in a Parr reactor using a MgO catalyst
at 340 °C, with mixing rate of 300 rpm.
The ketone mixture was hydrogenated in the HDO step in a Parr reactor as in
Example 1, and light fractions were separated by distillation from the final
product under reduced pressure. In comparison to other Examples, branched
paraffins having longer chains were obtained as products. Hydrocarbon
components may also be produced in a similar manner from other fatty acids or
fatty acid methyl esters of plant, animal and fish origin and dicarboxylic acids.
Either the fatty acids, or alternatively the wax obtained after ketonisation and
hydrodeoxygenation may be subjected to isomerization.




HC-CDW = hydrocracked, catalytically dewaxed base oil
Example 7
Preparation of a hydrocarbon component from tatty acids derived from palm oil
Palm oil was hydroIyzed. Fatty acids derived from palm oil were used as the
feedstock following selective prehydrogenation of the double bonds of said fatty
acids. The fatty acids were vaporized with nitrogen purge in a separate vaporizer
unit and ketonised continuously at atmospheric pressure, in a tubular reactor using
a MnO2 as catalyst. Temperature of the reactor was 380 °C, the WHSV of the feed
being 1 1/h-l.
The C31, C33, C35 ketone mixture obtained from the ketonisation stage was
hydrodeoxygenated continuously in a tubular fixed bed reactor using a dried and
activated NiMo/Al2O3 catalyst to give linear paraffins. Hydrodeoxygenation was

carried out under a pressure of 4 MPa (40 bar), at 270 °C and with WHSV of 1
1/h.
The linear paraffin wax obtained in the HDO step was isomerized continuously in
a tubular fixed bed reactor using a reduced Pt molecular sieve/Al2O3 catalyst to
give branched paraffins using a reduced Pt molecular sieve/Al2O3 catalyst.
Isomerization was performed at 340 °C, under a hydrogen pressure of 4 MPa until
the pour point of the product was below -15 °C. Finally, light fractions were
distilled under reduced pressure and separated.
Hydrocarbon components may also be produced in a similar way from other plant
and fish oils, and animal fats.



Example 8
Determination of the biological origin of the hydrocarbon component
Hydrocarbon component of biological origin was weighed into mineral oil based
Group III base oil, and mixed thoroughly. For the first sample, 0.5014 g of the
hydrocarbon component of biological origin was weighed, and base oil
component of the Group III was added in an amount to obtain a total weight of
10.0000 g; for the second sample, 1.0137 g of the hydrocarbon component of
biological origin was weighed, and base oil component of the Group III was
added in an amount to obtain a total weight of 10.0232 g. The measured results
are summarized in Table 7 below. Content of radioactive carbon (14C isotope) is
expressed as "percent modern carbon", based on the content of radioactive carbon
of the atmosphere in 1950. At present, the content of radioactive carbon of the
atmosphere is about 107 %. 813 C value shows the ratio of stable carbon isotopes
13C/l2C. By means of this value, the isotope fractionation found in our process
may be corrected. Actual results are presented in the last column.


Example 8
Carbon number distribution
The proportion of hydrocarbons in certain carbon number range of the base oil
product is dependent on distillation. In Figure 3 the carbon number distributions
of VHVI (413-520 °C cut) and the baseoils of invention (360-°C cut) are shown.
The carbon number distribution of the base oils according to invention is narrower
than that of conventional base oils when distillation is cut in similar manner at >
413 °C corresponding to C26 paraffin. In addition to the narrow carbon number
distribution, the baseoils of the invention contain also higher amount of higher
boiling fractions compared to the conventional product of same viscosity range
(KV100 about 4 cSt), as shown in Figure 3. The lower boiling components with
carbon number compounds enhance VI.

We claim
1. Base oil, characterized in that the base oil comprises branched hydrocarbons
having carbon numbers of at least C18, and it contains at least 90 % by weight of
saturated hydrocarbons, it contains mononaphthenes more than 5 % and fused
dinaphthenes and polynaphthenes not more than 1 % by weight, at least 50 % by weight
of the saturated hydrocarbons having width of the carbon number range of no more than
9 and the distillation range of the base oil being no more than 70°C.
2. The base oil as claimed in claim 1, wherein the base oil comprises at least 95 % by
weight of saturated hydrocarbons.
3. The base oil as claimed in claim 1 or 2, wherein at least 75 % by weight of the
saturated hydrocarbons have width of the carbon number range of no more than 9.
4. The base oil as claimed in any one of claims 1-3, wherein the base oil comprises at
least 97 % by weight of saturated hydrocarbons.
5. The base oil as claimed in any one of claims 1- 4, wherein at least 50 % by weight
of the saturated hydrocarbons have width of the carbon number range of no more than 7,
preferably no more than 5.
6. The base oil as claimed in any one of claims 1-5, wherein the viscosity index of
said base oil is more than 115, preferably more than 120.

7. The base oil as claimed in any one of claims 1-6, wherein the 14C isotope content of
the total carbon content in base oil is at least 50 %, preferably at least 90 % on the basis
of radioactive carbon content in the atmosphere in the year 1950 according to ASTM D
6866 - Standard Test Methods for Determing the Biobased Content of Solid, Liquid, and
Gaseous Samples Using Radiocarbon Analysis.
8. Process for producing base oil or the base oil as claimed in any of the claims 1-7,
wherein the process comprises ketonisation, hydrodeoxygenation and isomerization steps,
using a feedstock comprising at least one compound selected from the group consisting
of triglycerides, carboxylic acids having a carbon number C1-C38, esters of C1-C38
carboxylic acids with C1-C11 alcohols, C1-C38 alcohols, C1-C38 aldehydes, C1-C38
carboxylic acid anhydrides, and metal salts of C1-C38 carboxylic acids, esters of C1 -
C38 carboxylic acids with C12-C38 alcohols, natural waxes, dicarboxylic acids and

polyols, and the ketonisation is carried out in the presence of metal oxide catalyst under a
pressure from 0 to 10 MPa and at a temperature ranging from 100 to 500 °C, the
ketonisation product is hydrodeoxygenated in the presence of a hydrodeoxygenation
catalyst containing at least one component selected from the group consisting of metals
of the Group VIII or Group VIA of the periodic system of the elements and a support,
under a hydrogen pressure ranging from 0.1 to 20 MPa at a temperature ranging from 100
to 500 °C, and the isomerization is carried out in the presence of a isomerization catalyst
containing a metal of the Group VIII of the periodic system of the elements and/or a
support, under a hydrogen pressure ranging from 0 to 20 MPa at a temperature ranging
from 100 to 500 °C.
9. The process as claimed in claim 8, wherein the feedstock comprises at least one
compound selected from the group consisting of C4-C24 fatty acids, C4-C24 fatty acid
alkyl esters, C4-C24 fatty acid metal salts, C4-C24 fatty alcohols, C4-C24 fatty
aldehydes, esters of C4-C24 fatty acids with C12-C24 fatty alcohols and C4-C24 fatty
acid anhydrides derived from starting material of biological origin, and mixtures thereof.
10. The process as claimed in claim 8 or 9, wherein said starting material of biological
origin is selected from the group consisting of plant fats, plant oils, plant waxes, animal
fats, animal oils, animal waxes, fish fats, fish oils, fish waxes, and
a. free fatty acids or fatty acids obtained by hydrolysis, acid
transesterification or pyrolysis reactions from plant fats, plant oils, plant waxes,
animal fats, animal oils, animal waxes, fish fats, fish oils, fish waxes, and
b. esters obtained by transesterification from plant fats, plant oils, plant
waxes, animal fats, animal oils, animal waxes, fish fats, fish oils, fish waxes, and
c. fatty acid alkyl esters obtained by esterification of alcohols with fatty
acids of plant, animal and fish origin, and
d. fatty acid metal salts obtained by saponification of free fatty acids,
plant fats, plant oils, plant waxes, animal fats, animal oils, animal waxes, fish fats,
fish oils, fish waxes, and
e. alcohols and aldehydes obtained as reduction or hydrogenolysis
products of free fatty acids, or fatty acids from plant fats, plant oils, plant waxes,
animal fats, animal oils, animal waxes, fish fats, fish oils, fish waxes, and
f. fatty alcohols obtained by hydrolysis, transesterification and pyrolysis
from waxes of biological origin, and

g. anhydrides of fatty acids from plant fats, plant oils, plant waxes,
animal fats, animal oils, animal waxes, fish fats, fish oils, fish waxes, and
h. waste and recycled food grade fats and oils, and fats, oils and waxes
obtained by genetic engineering, and
i. mixtures of said materials.
11. The process as claimed in any one of claims 8-10, wherein a hydrocarbon or a
mixture of hydrocarbons is added to the feedstock and/or as a diluent to process steps.
12. The process as claimed in any one of claims 8-11, wherein the ketonisation is
performed at a pressure from 0.1 to 5 MPa at a temperature ranging from 100 to 400 °C.
13. The process as claimed in any one of claims 8-12, wherein the metal oxide
catalysts is Na, Mg, K, Ca, Sc, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Y, Zr, Mo, Rh, Cd, Sn, La,
Pb, Bi or a rare earth metal oxide catalyst on or without a support, preferably the metal
oxide is molybdenum, manganese and/or magnesium oxide.
14. The process as claimed in claim 13, wherein the support is laterite, bauxite,
titanium dioxide, silica and/or aluminium oxide.
15. The process as claimed in any one of claims 8-14, wherein the hydrodeoxygenation
is performed under a hydrogen pressure ranging from 1 to 15 MPa at a temperature
ranging from 150 to 400 °C.
16. The process as claimed in any one of claims 8-15, wherein the hydrodeoxygenation
catalyst contains at least one component selected from the group consisting of Pd, Pt, Ni,
NiMo and CoMo metals, and active carbon, alumina and/or silica support.
17. The process as claimed in any one of claims 8-16, wherein after the
hydrodeoxygenation hydroisomerization is carried out under a hydrogen pressure ranging
from 1 to 15 MPa at a temperature ranging from 200 to 400 °C.
18. The process as claimed in claim 17, wherein the catalyst of the hydroisomerization
step contains a molecular sieve and a Pd, Pt or Ni metal and/or a support, said support
being alumina and/or silica.
19. The process as claimed in any one of claims 8-18, wherein the isomerization is
performed before the ketonisation using carboxylic acid or carboxylic acid alkyl ester as

feed, at a temperature from 150 - 350 °C, preferably from 200 to 290 °C at a pressure of 0
- 5 MPa, preferably 0.1-2 MPa in the presence of an isomerization catalyst.
20. The process as claimed in claim 19, wherein the isomerization is carried out in the
presence of an acidic catalyst, the catalyst being preferably a zeolite of the pentasil or
mordenite type.
21. The process as claimed in claim 19 or 20, wherein from 0 to 8 %, preferably from 1
to 3 % of water or alcohol is added to the feedstock.
22. The process as claimed in any one of claims 19-21, wherein prior to the
ketonisation, prehydrogenation is performed under a hydrogen pressure between 0.1 and
20 MPa, preferably between 1 and 15 MPa, a temperature between 50 and 400 °C,
preferably between 100 and 300 °C, in the presence of a catalyst.
23. The process as claimed in claim 22, wherein the catalyst contains at least one
component selected from the group consisting of metals of the Group VIII and VIA of
the periodic system of the elements, and a support, the catalyst being preferably a
supported Pd, Pt, Ni, Ru, Rh, NiMo or CoMo catalyst, the support being active carbon,
alumina and/or silica.
24. The process as claimed in any one of claims 8-23, wherein as by-product a diesel
component or gasoline is produced.


(54) Title: PROCESS FOR PRODUCING A HYDROCARBON COMPONENT
(57) Abstract: The invention relates to a process for producing a new type of high-quality hydrocarbon base oil of biological origin.
The process of the invention comprises ketonisation, hydrodeoxygenation, and isomerization steps. Fatty acids and/or fatty acid
esters based on a biological raw material are preferably used as the feedstock.

Documents:

http://ipindiaonline.gov.in/patentsearch/GrantedSearch/viewdoc.aspx?id=7ktn9MOGLG96oUQsqROPsQ==&loc=wDBSZCsAt7zoiVrqcFJsRw==


Patent Number 268693
Indian Patent Application Number 2263/KOLNP/2008
PG Journal Number 38/2015
Publication Date 18-Sep-2015
Grant Date 11-Sep-2015
Date of Filing 09-Jun-2008
Name of Patentee NESTE OIL OYJ
Applicant Address KEILARANTA 21, FI-02150 ESPOO, FINLAND
Inventors:
# Inventor's Name Inventor's Address
1 KOIVUSALMI EIJA TARAMAENTIE 31, FI-06830 KULLOONKYLA, FINLAND
2 MYLLYOJA JUKKA LAMMASTIE 14 C 12, FI-01710 VANTAA, FINLAND
3 AALTO PEKKA EEMELINTIE 2, FI-06400 PORVOO, FINLAND
4 MOILANEN JUHA SINIKELLONKUJA 6, FI-06100 PORVOO, FINLAND
5 SELIN JOHAN-FREDRIK ISONMASTONTIE 15 D, FI-00980 HELSINKI, FINLAND
6 JAKKULA JUHA PAASIKIVENKATU 14 A 12, FI-04200 KERAVA, FINLAND
PCT International Classification Number C10G 3/00
PCT International Application Number PCT/FI2006/050548
PCT International Filing date 2006-12-12
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 20055666 2005-12-12 Finland
2 60/749036 2005-12-12 Finland